Resist composition and patterning process

ABSTRACT

The present invention relates to: a resist composition such as a chemically amplified resist composition for providing an excellent pattern profile even at a substrate-side boundary face of resist, in addition to a higher resolution in photolithography for micro-fabrication, and particularly in photolithography adopting, as an exposure source, KrF laser, ArF laser, F 2  laser, ultra-short ultraviolet light, electron beam, X-rays, or the like; and a patterning process utilizing the resist composition. The present invention provides a chemically amplified resist composition comprising one or more kinds of amine compounds or amine oxide compounds (except for those having a nitrogen atom of amine or amine oxide included in a ring structure of an aromatic ring) at least having a carboxyl group and having no hydrogen atoms covalently bonded to a nitrogen atom as a basic center.

This is a Continuation of application Ser. No. 12/457,192 filed Jun. 3,2009. The disclosure of the prior application is hereby incorporated byreference herein in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a photoresist to be used formicro-fabrication of semiconductors, photomask blanks, and the like, andparticularly to a chemically amplified positive or negative resist to beused for precisely conducting micro-fabrication by ultraviolet rays,EUV, electron beam exposure at wavelengths of 300 nm or shorter.

2. Description of the Related Art

It is known that finer pattern rules are demanded with highly integratedLSI's providing highly increased speeds. This has correspondingly led tolargely changed exposure methods and resist compositions, andparticularly, KrF, ArF excimer laser light, electron beam, and the likeare used as exposure light sources upon conduction of lithography ofpatterns at 0.2 μm or less, in a manner to adopt chemically amplifiedphotoresists, which exhibit excellent sensitivities to such high energyradiations and provide higher resolutions.

However, chemically amplified resist compositions are defectivelyaccompanied by: a problem (called PED [Post Exposure Delay]) such thatextended standing-still periods from exposure to PEB (post-exposurebake) lead to T-topped shapes of line patterns upon formation ofpositive patterns, i.e., lead to patterns having thickened upperportions; or a problem, which is a so-called footing phenomenon wherepatterns are thickened near a substrate, such as a substrate formed withmetal like Al, Cr, or the like, or a basic substrate, particularly asilicon nitride substrate or titanium nitride substrate. The T-toppedphenomenon is considered to be due to a decreased solubility of a resistfilm surface, while the footing at a substrate surface is considered tobe due to a decreased solubility of the resist near the substrate.

In turn, upon formation of a negative pattern, there is caused aso-called undercut phenomenon where a cross-linking reaction of anegative resist is decreased near a substrate such that the pattern issubjected to constriction at a substrate-side boundary face of resist.

In case of chemically amplified positive resist compositions, the reasonof the problem of PED or footing profile at a substrate surface isconsidered to be largely affected by a basic compound in air or at asubstrate surface. Acids generated by exposure at a resist film surfacereact with basic compounds in air and are inactivated, such that longerstanding-still times until PEB correspondingly increase amounts of acidsto be inactivated, to scarcely cause decomposition of acid labilegroups. As such, hardly soluble layers are formed at surfaces ofresists, so that patterns are brought into T-topped shapes,respectively.

Against this problem, it is well known that addition of anitrogen-containing compound allows for restriction of an influence ofbasic compounds in air, and this is also effective to PED (see JapanesePatent Application Laid-open (kokai) No. H05-232706, for example).Particularly, amine compounds or amide compounds have been noticed asnitrogen-containing compounds having higher addition effects, andnumerous concrete compounds have been proposed.

Although it has been proposed to use a relatively weak base against theabove-mentioned T-topped problem, the weak base is insufficient forcontrol of deprotection reaction within a resist film, i.e., for controlof diffusion of acids for causing a catalytic reaction, in case ofadoption of acid labile groups having higher reactivities to be used forobtaining higher resolutions. Addition of weak base particularly resultsin progression of dark reaction in PED even at an non-exposed area,thereby causing a decrease of line dimension (slimming) and a filmdecrease at line surface in PED. To solve this problem, it is desirableto add a strong base. However, stronger basicities are not necessarilypreferable, such that a sufficient effect can not be obtained even byaddition of DBU (1,8-diazabicyclo[5.4.0]-7-undecene) or DBN(1,5-diazabicyclo[4.3.0]-5-nonene), which are regarded as being superbase, or proton sponge (1,8-bis(dimethylamino)naphthalene), orquaternary ammonium hydroxides such as tetramethylammonium hydroxide.

Meanwhile, it is effective to add a nitrogen-containing compound havingan improved effect for capturing generated acids, for increasedcontrasts for achieving higher resolutions. Although a dissociationconstant between acid and base in water can be explained by pKa, anacid-capturing ability and pKa of a nitrogen-containing compound in aresist film are not directly related to each other. This has been statedby Hatakeyama et al., in a J. Hatakeyama, et. al., J. Photopolym. Sci.Technol., 13(4), 519-524 (2000). It has been additionally recognizedthat types of nitrogen-containing organic compounds to be used largelyaffect pattern profile.

Concerning pattern profile in substrate-side boundary face of resists,although problems of footing profile and undercut are improved byaddition of base, the improvement is insufficient. While furtherincrease of addition amounts of base will result in further improvement,there is caused a tradeoff problem of a considerably deterioratedsensitivity.

In turn, to solve a problem of footing profile of a resist pattern on alight-shielding film of a photomask upon fabrication of thelight-shielding film, it has been disclosed that formation of apolymeric undercoat on a sputteredly deposited metal compound results inobtainment of a pattern without footing (Japanese Patent ApplicationLaid-open (kokai) No. 2007-171520). However, the countermeasure on asubstrate side requires an increased number of steps for processing, andis problematic not only in a complicated process but also in anincreased production cost.

In turn, to improve footing on a Cr substrate of a mask blank, there hasbeen proposed a resist composition combined with a basic additiveincluding a base, which is solid at a room temperature (20 to 25° C.)and a low vapor pressure base, which is liquid at a room temperature(Japanese Patent Application Laid-open (kohyou) No. 2007-522524).Because production processes have been problematically complicated whenfooting is to be solved by the countermeasure on a substrate side, it isimportant that the problem is solved by a countermeasure on a resistcomposition side. However, adoption of the low vapor pressure base leadsto evaporation of the base at a prebaking temperature, therebyoccasionally causing a sensitivity change by a concentration change.This makes it difficult to keep dimensions of a pattern with higherprecision.

Further, at an early stage of elaboration of chemically amplifiedresists during a proposal period of various basic compounds, there hasbeen proposed addition of amino acid, 3-aminopyrazine-2-carboxylic acid,or the like, as a compound having an amino group and a carboxyl group(Japanese Patent Application Laid-open (kokai) No. H05-289340). However,there have not been found important proposals thereafter to use such anamine compound having a carboxyl group, and such a situation isconsidered to be due to failure of remarkable effects by such usage inseeking for a higher resolution.

SUMMARY OF THE INVENTION

The present invention has been carried out in view of the abovecircumstances, and it is therefore an object of the present invention toprovide: a resist composition for (1) a chemically amplified positiveresist composition, which is made soluble in alkali upon elimination ofan acid labile group by an acid catalyst, and (2) a chemically amplifiednegative resist composition, which is made insoluble in alkali by anacid catalyst and/or which is made insoluble in alkali by reaction witha crosslinking agent by an acid catalyst, such that the resistcomposition provides, by addition of the above-mentioned basiccomponent, an excellent pattern profile even at a substrate-sideboundary face of resist, in addition to a higher resolution inphotolithography for micro-fabrication, and particularly inphotolithography adopting, as an exposure source, KrF laser, ArF laser,F₂ laser, ultra-short ultraviolet light, electron beam, X-rays, or thelike; and a patterning process utilizing the resist composition.

To achieve the above object, the present inventors have earnestlyconducted investigations to narrowly carry out the present invention, byresultingly finding that: adoption of an amine compound or amine oxidecompound having a carboxyl group and having no hydrogen atoms covalentlybonded to a nitrogen atom as a basic center as a basic component, to beadded into a resist composition, allows for formation of a resist film,which resist film is capable of remarkably improving perpendicularity ofa line pattern even at a substrate-side boundary face of resist inaddition to a higher resolution, and which resist film provides anexcellent etching resistance for preserving a pattern profile.

Namely, the present invention resides in a chemically amplified resistcomposition comprising one or more kinds of amine compounds or amineoxide compounds (except for those having a nitrogen atom of amine oramine oxide included in a ring structure of an aromatic ring) at leasthaving a carboxyl group and having no hydrogen atoms covalently bondedto a nitrogen atom as a basic center.

Although there has been already proposed (see Japanese PatentApplication Laid-open (kokai) No. H05-289340) addition of amino acid,3-aminopyrazine-2-carboxylic acid and the like concerning addition of acompound having an amino group and a carboxyl group, it is impossible toattain a higher resolution by such compounds even when they areintendedly used to do so. Nonetheless, it is possible to realize notonly a higher resolution but also an excellent pattern profileexhibiting a less dependency on a material of a substrate surface, incase of adopting, as a basic component, the amine compound or amineoxide compound having a carboxyl group and having no hydrogen atomscovalently bonded to a nitrogen atom as a basic center, according to thepresent invention.

In this case, the nitrogen atom of the amine compound or amine oxidecompound having a carboxyl group and having no hydrogen atoms covalentlybonded to a nitrogen atom as a basic center, preferably has three singlebonds combined to different carbon atoms, respectively.

Further, as a desirable configuration, the amine compound having acarboxyl group and having no hydrogen atoms covalently bonded to anitrogen atom as a basic center, may include an amine compound having acarboxyl group represented by the following general formula (1):

Addition of such an amine compound is particularly advantageous toformation of a resist pattern exhibiting an excellent profile having aless dependency on a substrate:

-   -   wherein R₁ and R₂ are each a linear, branched, or cyclic alkyl        group having 1 to 20 carbon atoms, an aryl group having 6 to 20        carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, or an alkylthio-alkyl group having 1 to 10        carbon atoms;    -   R₁ and R₂ may be bonded to each other to form a ring structure;    -   R₃ is a hydrogen atom, a linear, branched, or cyclic alkyl group        having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon        atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, an alkylthio-alkyl group having 1 to 10        carbon atoms, or a halogen group; and    -   R₄ is a linear, branched, or cyclic alkylene group having 0 to        20 carbon atoms, or an arylene group having 6 to 20 carbon        atoms.

Furthermore, as one configuration, the amine oxide compound having acarboxyl group and having no hydrogen atoms covalently bonded to anitrogen atom as a basic center, may include an amine oxide compoundhaving a carboxyl group represented by the following general formula(2):

Addition of such an amine oxide compound is also particularlyadvantageous to formation of a resist pattern exhibiting an excellentprofile having a less dependency on a substrate:

-   -   wherein R₁ and R₂ are each a linear, branched, or cyclic alkyl        group having 1 to 20 carbon atoms, an aryl group having 6 to 20        carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, or an alkylthio-alkyl group having 1 to 10        carbon atoms;    -   R₁ and R₂ may be bonded to each other to form a ring structure;    -   R₃ is a hydrogen atom, a linear, branched, or cyclic alkyl group        having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon        atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, an alkylthio-alkyl group having 1 to 10        carbon atoms, or a halogen group; and    -   R₄ is a linear, branched, or cyclic alkylene group having 0 to        20 carbon atoms, or an arylene group having 6 to 20 carbon        atoms.

As another configuration, the amine compound having a carboxyl group andhaving no hydrogen atoms covalently bonded to a nitrogen atom as a basiccenter, may include an amine compound having carboxyl group representedby the following general formula (3):

Addition of such an amine compound is also particularly advantageous toformation of a resist pattern exhibiting an excellent profile having aless dependency on a substrate:

-   -   wherein R₅ is a linear or branched substitutable alkylene group        having 2 to 20 carbon atoms, wherein the alkylene group may        include, between its carbon atoms, one or more carbonyl groups,        ether groups, ester groups, or sulfides; and    -   R₆ is a linear, branched, or cyclic alkylene group having 1 to        20 carbon atoms, or an arylene group having 6 to 20 carbon        atoms.

Namely, the amine compound or amine oxide compound having a carboxylgroup and having no hydrogen atoms covalently bonded to a nitrogen atomas a basic center, may include an amine compound or amine oxide compoundhaving a carboxyl group represented by the following general formula(1), (2), or (3):

-   -   wherein R₁ and R₂ are each a linear, branched, or cyclic alkyl        group having 1 to 20 carbon atoms, an aryl group having 6 to 20        carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, or an alkylthio-alkyl group having 1 to 10        carbon atoms;    -   R₁ and R₂ may be bonded to each other to form a ring structure;    -   R₃ is a hydrogen atom, a linear, branched, or cyclic alkyl group        having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon        atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, an alkylthio-alkyl group having 1 to 10        carbon atoms, or a halogen group; and    -   R₄ is a linear, branched, or cyclic alkylene group having 0 to        20 carbon atoms, or an arylene group having 6 to 20 carbon        atoms.

-   -   wherein R₁ and R₂ are each a linear, branched, or cyclic alkyl        group having 1 to 20 carbon atoms, an aryl group having 6 to 20        carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, or an alkylthio-alkyl group having 1 to 10        carbon atoms;    -   R₁ and R₂ may be bonded to each other to form a ring structure;    -   R₃ is a hydrogen atom, a linear, branched, or cyclic alkyl group        having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon        atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, an alkylthio-alkyl group having 1 to 10        carbon atoms, or a halogen group; and    -   R₄ is a linear, branched, or cyclic alkylene group having 0 to        20 carbon atoms, or an arylene group having 6 to 20 carbon        atoms.

-   -   wherein R₅ is a linear or branched substitutable alkylene group        having 2 to 20 carbon atoms, wherein the alkylene group may        include, between its carbon atoms, one or more carbonyl groups,        ether groups, ester groups, or sulfides; and    -   R₆ is a linear, branched, or cyclic alkylene group having 1 to        20 carbon atoms, or an arylene group having 6 to 20 carbon        atoms.

The chemically amplified resist composition of the present invention mayfurther comprise one or more kinds of amine compounds each representedby the following general formula (4):

Combination of such bases is sometimes advantageous, depending oncombination of polymers, acid generators, and the like:

-   -   wherein R₇, R₈, and R₉ are each a hydrogen atom, a linear,        branched, or cyclic alkyl group having 1 to 20 carbon atoms, an        aryl group having 6 to 20 carbon atoms, an aralkyl group having        7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon        atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an        acyloxyalkyl group having 2 to 10 carbon atoms, or an        alkylthio-alkyl group having 1 to 10 carbon atoms; and    -   two of R₇, R₈, and R₉ may be bonded to form a ring structure or        an aromatic ring.

The resist composition may further comprise one or more kinds of amineoxide compounds each represented by the following general formula (5):

Combination with such an amine oxide compound is sometimes advantageous:

-   -   wherein R₇, R₈, and R₉ are each a hydrogen atom, a linear,        branched, or cyclic alkyl group having 1 to 20 carbon atoms, an        aryl group having 6 to 20 carbon atoms, an aralkyl group having        7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon        atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an        acyloxyalkyl group having 2 to 10 carbon atoms, or an        alkylthio-alkyl group having 1 to 10 carbon atoms; and    -   two of R₇, R₈, and R₉ may be bonded to form a ring structure or        an aromatic ring.

Namely, the chemically amplified resist composition may further compriseone or more kinds of amine compounds or amine oxide compounds eachrepresented by the following general formula (4) or general formula (5):

-   -   wherein R₇, R₈, and R₉ are each a hydrogen atom, a linear,        branched, or cyclic alkyl group having 1 to 20 carbon atoms, an        aryl group having 6 to 20 carbon atoms, an aralkyl group having        7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon        atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an        acyloxyalkyl group having 2 to 10 carbon atoms, or an        alkylthio-alkyl group having 1 to 10 carbon atoms; and    -   two of R₇, R₈, and R₉ may be bonded to form a ring structure or        an aromatic ring.

-   -   wherein R₇, R₈, and R₉ are each a hydrogen atom, a linear,        branched, or cyclic alkyl group having 1 to 20 carbon atoms, an        aryl group having 6 to 20 carbon atoms, an aralkyl group having        7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon        atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an        acyloxyalkyl group having 2 to 10 carbon atoms, or an        alkylthio-alkyl group having 1 to 10 carbon atoms; and    -   two of R₇, R₈, and R₉ may be bonded to form a ring structure or        an aromatic ring.

Further, the present invention provides a chemically amplified positiveresist composition containing, as main components:

-   -   (A1) a base resin insoluble or hardly soluble in alkali, having        an acidic functional group protected by an acid labile group,        wherein the resin is made to be soluble in alkali when the acid        labile group is eliminated;    -   (B) an acid generator; and    -   (C) an amine compound or amine oxide compound (except for those        having a nitrogen atom of amine or amine oxide included in a        ring structure of an aromatic ring) at least having a carboxyl        group and having no hydrogen atoms covalently bonded to a        nitrogen atom as a basic center as a basic component.

The amine compound or amine oxide compound having a carboxyl group andhaving no hydrogen atoms covalently bonded to a nitrogen atom as a basiccenter, is extremely effective as a basic substance to be added into apositive resist composition.

In this case, the nitrogen atom of (C) the amine compound or amine oxidecompound having a carboxyl group and having no hydrogen atoms covalentlybonded to a nitrogen atom as a basic center, preferably has three singlebonds combined to different carbon atoms, respectively.

The amine compound or amine oxide compound having a carboxyl group andhaving no hydrogen atoms covalently bonded to a nitrogen atom as a basiccenter of (C), may include an amine compound or amine oxide compoundhaving a carboxyl group represented by the following general formula(1), (2), or (3)

-   -   wherein R₁ and R₂ are each a linear, branched, or cyclic alkyl        group having 1 to 20 carbon atoms, an aryl group having 6 to 20        carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, or an alkylthio-alkyl group having 1 to 10        carbon atoms;    -   R₁ and R₂ may be bonded to each other to form a ring structure;    -   R₃ is a hydrogen atom, a linear, branched, or cyclic alkyl group        having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon        atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, an alkylthio-alkyl group having 1 to 10        carbon atoms, or a halogen group; and    -   R₄ is a linear, branched, or cyclic alkylene group having 0 to        20 carbon atoms, or an arylene group having 6 to 20 carbon        atoms.

-   -   wherein R₁ and R₂ are each a linear, branched, or cyclic alkyl        group having 1 to 20 carbon atoms, an aryl group having 6 to 20        carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, or an alkylthio-alkyl group having 1 to 10        carbon atoms;    -   R₁ and R₂ may be bonded to each other to form a ring structure;    -   R₃ is a hydrogen atom, a linear, branched, or cyclic alkyl group        having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon        atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, an alkylthio-alkyl group having 1 to 10        carbon atoms, or a halogen group; and    -   R₄ is a linear, branched, or cyclic alkylene group having 0 to        20 carbon atoms, or an arylene group having 6 to 20 carbon        atoms.

-   -   wherein R₅ is a linear or branched substitutable alkylene group        having 2 to 20 carbon atoms, wherein the alkylene group may        include, between its carbon atoms, one or more carbonyl groups,        ether groups, ester groups, or sulfides; and    -   R₆ is a linear, branched, or cyclic alkylene group having 1 to        20 carbon atoms, or an arylene group having 6 to 20 carbon        atoms.

Addition of such an amine compound or amine oxide compound isparticularly advantageous to formation of a resist pattern exhibiting anexcellent profile having a less dependency on a substrate.

Furthermore, The chemically amplified positive resist composition mayfurther comprise one or more kinds of amine compounds or amine oxidecompounds each represented by the following general formula (4) orgeneral formula (5):

-   -   wherein R₇, R₈, and R₉ are each a hydrogen atom, a linear,        branched, or cyclic alkyl group having 1 to 20 carbon atoms, an        aryl group having 6 to 20 carbon atoms, an aralkyl group having        7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon        atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an        acyloxyalkyl group having 2 to 10 carbon atoms, or an        alkylthio-alkyl group having 1 to 10 carbon atoms; and    -   two of R₇, R₈, and R₉ may be bonded to form a ring structure or        an aromatic ring.

-   -   wherein R₇, R₈, and R₉ are each a hydrogen atom, a linear,        branched, or cyclic alkyl group having 1 to 20 carbon atoms, an        aryl group having 6 to 20 carbon atoms, an aralkyl group having        7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon        atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an        acyloxyalkyl group having 2 to 10 carbon atoms, or an        alkylthio-alkyl group having 1 to 10 carbon atoms; and    -   two of R₇, R₈, and R₉ may be bonded to faun a ring structure or        an aromatic ring.

Combination of such bases is sometimes advantageous, depending oncombination of polymers, acid generators, and the like.

Moreover, the present invention provides a chemically amplified negativeresist composition containing, as main components:

-   -   (A2) a base resin, which is soluble in alkali and which is made        insoluble in alkali with the aid of an acid catalyst; and/or, a        combination of a base resin with a crosslinking agent, which        base resin is soluble in alkali and is made insoluble in alkali        via reaction with the crosslinking agent with the aid of an acid        catalyst;    -   (B) an acid generator; and    -   (C) an amine compound or amine oxide compound (except for those        having a nitrogen atom of amine or amine oxide included in a        ring structure of an aromatic ring) at least having a carboxyl        group and having no hydrogen atoms covalently bonded to a        nitrogen atom as a basic center as a basic component.

The amine compound or amine oxide compound having a carboxyl group andhaving no hydrogen atoms covalently bonded to a nitrogen atom as a basiccenter, is also extremely effective as a basic substance to be addedinto a negative resist composition.

In this case, the nitrogen atom of (C) the amine compound or amine oxidecompound having a carboxyl group and having no hydrogen atoms covalentlybonded to a nitrogen atom as a basic center, preferably has three singlebonds combined to different carbon atoms, respectively.

The amine compound or amine oxide compound having a carboxyl group andhaving no hydrogen atoms covalently bonded to a nitrogen atom as a basiccenter of (C), may include an amine compound or amine oxide compoundhaving a carboxyl group represented by the following general formula(1), (2), or (3)

-   -   wherein R₁ and R₂ are each a linear, branched, or cyclic alkyl        group having 1 to 20 carbon atoms, an aryl group having 6 to 20        carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, or an alkylthio-alkyl group having 1 to 10        carbon atoms;    -   R₁ and R₂ may be bonded to each other to form a ring structure;    -   R₃ is a hydrogen atom, a linear, branched, or cyclic alkyl group        having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon        atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, an alkylthio-alkyl group having 1 to 10        carbon atoms, or a halogen group; and    -   R₄ is a linear, branched, or cyclic alkylene group having 0 to        20 carbon atoms, or an arylene group having 6 to 20 carbon        atoms.

-   -   wherein R₁ and R₂ are each a linear, branched, or cyclic alkyl        group having 1 to 20 carbon atoms, an aryl group having 6 to 20        carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, or an alkylthio-alkyl group having 1 to 10        carbon atoms;    -   R₁ and R₂ may be bonded to each other to form a ring structure;    -   R₃ is a hydrogen atom, a linear, branched, or cyclic alkyl group        having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon        atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, an alkylthio-alkyl group having 1 to 10        carbon atoms, or a halogen group; and    -   R₄ is a linear, branched, or cyclic alkylene group having 0 to        20 carbon atoms, or an arylene group having 6 to 20 carbon        atoms.

-   -   wherein R₅ is a linear or branched substitutable alkylene group        having 2 to 20 carbon atoms, wherein the alkylene group may        include, between its carbon atoms, one or more carbonyl groups,        ether groups, ester groups, or sulfides; and    -   R₆ is a linear, branched, or cyclic alkylene group having 1 to        20 carbon atoms, or an arylene group having 6 to 20 carbon        atoms.

Addition of such an amine compound or amine oxide compound isparticularly advantageous to formation of a resist pattern exhibiting anexcellent profile having a less dependency on a substrate.

Furthermore, The chemically amplified negative resist composition mayfurther comprise one or more kinds of amine compounds or amine oxidecompounds each represented by the following general formula (4) orgeneral formula (5):

-   -   wherein R₇, R₈, and R₉ are each a hydrogen atom, a linear,        branched, or cyclic alkyl group having 1 to 20 carbon atoms, an        aryl group having 6 to 20 carbon atoms, an aralkyl group having        7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon        atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an        acyloxyalkyl group having 2 to 10 carbon atoms, or an        alkylthio-alkyl group having 1 to 10 carbon atoms; and    -   two of R₇, R₈, and R₉ may be bonded to form a ring structure or        an aromatic ring.

-   -   wherein R₇, R₈, and R₉ are each a hydrogen atom, a linear,        branched, or cyclic alkyl group having 1 to 20 carbon atoms, an        aryl group having 6 to 20 carbon atoms, an aralkyl group having        7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon        atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an        acyloxyalkyl group having 2 to 10 carbon atoms, or an        alkylthio-alkyl group having 1 to 10 carbon atoms; and    -   two of R₇, R₈, and R₉ may be bonded to form a ring structure or        an aromatic ring.

Combination of such bases is sometimes advantageous, depending oncombination of polymers, acid generators, and the like.

Furthermore, the present invention provides a resist patterning processcomprising, at least, a steps of:

-   -   coating the above described resist composition onto a processing        substrate, and heating it to thereby eliminate an excessive        solvent component remaining in the coated film, to obtain a        resist film;    -   conducting pattern exposure by a high energy radiation; and    -   conducting, after a post-exposure baking treatment as required,        development by a developer.

As a particularly useful configuration of a resist patterning process,the present invention provides a patterning process comprising, atleast, a steps of:

-   -   coating the above described resist composition onto a mask        blanks formed with a chromium compound film;    -   conducting, after a heat treatment, pattern exposure by a high        energy radiation through a photomask, or pattern exposure by        high energy radiation beam;    -   conducting, after a heat treatment as required, development by a        developer.

Although it is extremely difficult to control a profile of a resistpattern near its boundary face on a chromium compound of a chromiumcompound film, it is possible to form a resist pattern having adesirable profile by adopting the resist patterning process of thepresent invention.

The present invention is configured to blend the amine compound or amineoxide compound, having a carboxyl group and having no hydrogen atomscovalently bonded to a nitrogen atom as a basic center as a basiccomponent, into the resist composition, so that the resist compositionis allowed to provide remarkably improve perpendicularity of a linepattern even at a substrate-side boundary face of resist, in addition toa higher resolution, and provide an excellent etching resistance forpreserving a pattern profile. Particularly, it becomes possible toprovide: a chemically amplified resist composition containing an aminecompound or amine oxide compound having a carboxyl group, which resistcomposition is desirable as a fine pattern forming, material forproduction of a VLSI and a photomask; and a patterning process utilizingthe resist composition.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Although embodiments of the present invention will be explained indetail, the present invention is not limited thereto.

The present inventors have earnestly conducted investigation of anunknown compound, which is to be blended into a resist composition tothereby provide an excellent pattern profile at a substrate-sideboundary face of resist, in addition to a higher resolution. As aresult, there has been obtained a chemically amplified photoresistcomposition, which provides an excellent pattern profile even at asubstrate-side boundary face of resist, in addition to a higherresolution. The present invention has been narrowly carried out in amanner that, although examples of such amine compound or amine oxidecompound having a carboxyl group and having no hydrogen atoms covalentlybonded to a nitrogen atom as a basic center, include compounds or oxidecompounds of amines (so-called tertiary amines) having substituted threedifferent carbon atoms, and compounds or oxide compounds of imineshaving substituted two different carbon atoms; it is found that theamine compounds or amine oxide compounds having a carboxyl group andhaving no hydrogen atoms covalently bonded to a nitrogen atom as a basiccenter represented by the following general formulae (1) to (3), can bereadily obtained at higher yields, and exhibit higher blending effects,respectively. Particularly, at substrate-side boundary faces of resistin case of conventional resist compositions, when development has beenconducted by a developer after a heat treatment as required afterexposure by electron beam; fine patterns are not resolved due to footingin case of positive-typed space patterns; while undercut is madeconsiderable in case of negative-typed line patterns such that narrowlyresolved fine patterns are made substantially meaningless due to patterncollapse caused by undercut after development. Such situations can beavoided by adoption of the resist composition of the present invention,while exhibiting an extremely enhanced improving effect.

Although the nitrogen-containing compounds to be blended in the resistcomposition of the present invention embrace the amine compounds oramine oxide compounds at least having a carboxyl group and having nohydrogen atoms covalently bonded to a nitrogen atom as a basic center asrepresented by the following general formulae (1) to (3) as noted above,the present invention is not limited thereto, and it is also possible toblend, into the resist composition, typically used amine compoundshaving no carboxyl groups and oxidizedly obtained compounds thereofhaving amine oxide structures, in addition to the amine compound oramine oxide compound having a carboxyl group and having no hydrogenatoms covalently bonded to a nitrogen atom as a basic center,

-   -   wherein R₁ and R₂ are each a linear, branched, or cyclic alkyl        group having 1 to 20 carbon atoms, an aryl group having 6 to 20        carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, or an alkylthio-alkyl group having 1 to 10        carbon atoms;    -   R₁ and R₂ may be bonded to each other to form a ring structure;    -   R₃ is a hydrogen atom, a linear, branched, or cyclic alkyl group        having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon        atoms, an aralkyl group having 7 to 20 carbon atoms, a        hydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl        group having 2 to 10 carbon atoms, an acyloxyalkyl group having        2 to 10 carbon atoms, an alkylthio-alkyl group having 1 to 10        carbon atoms, or a halogen group;    -   R₄ is a linear, branched, or cyclic alkylene group having 0 to        20 carbon atoms, or an arylene group having 6 to 20 carbon        atoms;    -   R₅ is a linear or branched substitutable alkylene group having 2        to 20 carbon atoms, wherein the alkylene group may include,        between its carbon atoms, one or more carbonyl groups, ether        groups, ester groups, or sulfides; and    -   R₆ is a linear, branched, or cyclic alkylene group having 1 to        20 carbon atoms, or an arylene group having 6 to 20 carbon        atoms.

Without any limitations, examples of an aryl group having 6 to 20 carbonatoms concretely include a phenyl group, naphthyl group, anthryl group,phenanthryl group, pyrenyl group, naphthacenyl group, and fluorenylgroup; examples of a linear, branched, or cyclic alkyl group having 1 to20 carbon atoms concretely include a methyl group, ethyl group, propylgroup, isopropyl group, butyl group, isobutyl group, t-butyl group,pentyl group, hexyl group, decyl group, cyclopentyl group, cyclohexylgroup, and decahydronaphthalenyl group; examples of an aralkyl grouphaving 7 to 20 carbon atoms concretely include a benzyl group, phenethylgroup, phenylpropyl group, naphthylmethyl group, naphthylethyl group,and anthracenylmethyl group; examples of a hydroxyalkyl group having 2to 10 carbon atoms concretely include a hydroxymethyl group,hydroxyethyl group, and hydroxypropyl group; examples of an alkoxyalkylgroup having 2 to 10 carbon atoms concretely include a methoxymethylgroup, 2-methoxyethyl group, ethoxymethyl group, 2-ethoxyethyl group,propoxymethyl group, 2-propoxyethyl group, butoxymethyl group,2-butoxyethyl group, amyloxymethyl group, 2-amyloxyethyl group,cyclohexyloxymethyl group, 2-cyclohexyloxyethyl group,cyclopentyloxymethyl group, 2-cyclopentyloxyethyl group, and isomers ofalkyl portions thereof, respectively; examples of an acyloxyalkyl grouphaving 2 to 10 carbon atoms concretely include a formyloxymethyl group,acetoxymethyl group, propionyloxymethyl group, butyryloxymethyl group,pivaloyloxymethyl group, cyclohexane carbonyloxymethyl group, anddecanoyloxymethyl group; and examples of an alkylthio-alkyl group having1 to 10 carbon atoms concretely include a methylthiomethyl group,ethylthiomethyl group, propylthiomethyl group, isopropylthiomethylgroup, butylthiomethyl group, isobutylthiomethyl group,t-butylthiomethyl group, t-amylthiomethyl group, decylthiomethyl group,and cyclohexylthiomethyl group.

Examples of the amine compounds having a carboxyl group and having nohydrogen atoms covalently bonded to a nitrogen atom as a basic center ofthe present invention as represented by the general formula (1) will beconcretely enumerated below, without limited thereto.

Namely, such examples include: o-dimethylaminobenzoic acid,p-dimethylaminobenzoic acid, m-dimethylaminobenzoic acid,p-diethylaminobenzoic acid, p-dipropylaminobenzoic acid,p-dibutylaminobenzoic acid, p-dibutylaminobenzoic acid,p-dipentylaminobenzoic acid, p-dihexylaminobenzoic acid,p-diethanolaminobenzoic acid, p-diisopropanolaminobenzoic acid,p-dimethanolaminobenzoic acid, 2-methyl-4-diethylaminobenzoic acid,2-methoxy-4-diethylaminobenzoic acid, 3-dimethylamino-2-naphthaleneacid, 3-diethylamino-2-naphthalene acid, 2-dimethylamino-5-bromobenzoicacid, 2-dimethylamino-5-chlorobenzoic acid,2-dimethylamino-5-iodobenzoic acid, 2-dimethylamino-5-hydroxybenzoicacid, 4-dimethylaminophenylacetic acid, 4-dimethylaminophenylpropionicacid, 4-dimethylaminophenylbutyric acid, 4-dimethylaminophenylmalicacid, 4-dimethylaminophenylpyruvic acid, 4-dimethylaminophenyllaceticacid, 2-(4-dimethylaminophenyl)benzoic acid, and244-(dibutylamino)-2-hydroxybenzoyl)benzoic acid.

The amine oxide compound having a carboxyl group and having no hydrogenatoms covalently bonded to a nitrogen atom as a basic center of thepresent invention as represented by the general formula (2) is obtainedby oxidizing each of the amine compounds concretely enumerated above,without limited thereto.

Further, examples of the amine compound having a carboxyl group andhaving no hydrogen atoms covalently bonded to a nitrogen atom as a basiccenter of the present invention as represented by the general formula(3) will be concretely enumerated below, without limited thereto.

Namely, examples thereof include 1-piperidinepropionic acid,1-piperidinebutric acid, 1-piperidinemalic acid, 1-piperidinepyruvicacid, 1-piperidinelactic acid, and the like.

The amine oxide structure represented by the general formula (2)embraces existing or novel compounds, and such compounds having an amineoxide structure are to be produced by selecting optimum techniquescorresponding to the structures of the compounds, respectively. Examplesthereof include a technique to adopt an oxidation reaction using anoxidizing agent for a nitrogen-containing compound, and a technique toadopt an oxidation reaction of a nitrogen-containing compound in adiluted solution of hydrogen peroxide, without limited thereto. Thiswill be explained in detail.

Exemplarily described below is a production method of anitrogen-containing alcohol compound by an esterification reaction, andthis is also applicable to synthesis of the compound represented by thegeneral formula (2).

In the above formula, although this reaction is an oxidation reaction ofamine adopting an oxidizing agent (m-chloroperbenzoic acid), thisreaction can be conducted by another oxidizing agent in a usual mannerof an oxidation reaction. After the reaction, mixed reaction productscan be purified by usual manners such as distillation, chromatography,recrystallization, and the like (for details thereof, see JapanesePatent Application Laid-open (kokai) No 2008-102383).

According to the present invention, it is expected that in the aminecompounds or amine oxide compounds having a carboxyl group in themolecule and having no hydrogen atoms covalently bonded to a nitrogenatom as a basic center, presence of a functional group substitutedlyprovided on the nitrogen atom realizes rapid capture of generated acidswhile the carboxyl group is located at a substrate side, so thatgenerated acids are prevented from diffusing into a substrate and frombeing inactivated; and as a result thereof; it is considered that thephotoresist including the added amine compound or amine oxide compoundhaving a carboxyl group of the present invention enables achievement ofa higher resolution, and a pattern profile excellent in perpendicularityat a substrate-side boundary face of resist. Further, it appears that,by selecting appropriate ones of possible structures of the aminecompounds or amine oxide compounds having a carboxyl group and having nohydrogen atoms covalently bonded to a nitrogen atom as a basic center ofthe present invention, volatilities, basic, acid capturing rates, anddiffusion velocities in resist of the amine compounds or amine oxidecompounds having a carboxyl group and having no hydrogen atomscovalently bonded to a nitrogen atom as a basic center of the presentinvention can be appropriately adjusted correspondingly to combinationsof resist polymers and acid generators to be used, thereby resultinglyenabling provision of an amine compound or amine oxide additive having acarboxyl group and having no hydrogen atoms covalently bonded to anitrogen atom as a basic center, which can optimally adjust propertiessuch as a pattern profile of a resist composition.

Since amine compounds like primary amines having hydrogen atomscovalently bonded to a nitrogen atom as a basic center, have no effectsfor overcoming a problem of footing profile or undercut, it is desirableto use tertiary amines to maximally exhibit the effect, which amineseach have no hydrogen atoms covalently bonded to a nitrogen atom as abasic center.

Further, although amine compounds such as 2-quinolinecarboxylic acid,nicotinic acid and the like having a nitrogen atom included in anaromatic ring have no hydrogen atoms covalently bonded to the nitrogenatom as a basic center, the compounds are weak base, so that thecarboxyl group of each compound is not considered to be located at asubstrate side. As such, it is impossible to prevent generated acidsfrom being diffused into a substrate and thus inactivated.

Usable as an organic solvent in the resist composition of the presentinvention are any organic solvents in which the base resin(s), the acidgenerator, other additives, and the like are soluble. Examples of theorganic solvents include: ketones such as cyclohexanone andmethyl-n-amylketone; alcohols such as 3-methoxybutanol,3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether,ethylene glycol monomethyl ether, propylene glycol monoethyl ether,ethylene glycol monoethyl ether, propylene glycol dimethyl ether, anddiethylene glycol dimethyl ether; esters such as propylene glycolmonomethyl ether acetate, propylene glycol monoethyl ether acetate,ethyl lactate, ethyl pyruvate, butyl acetate, methyl3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate,tert-butyl propionate, and propylene glycol mono-tert-butyl etheracetate; and lactones such as γ-butyrolactone; which can be used solely,or mixedly in two or more kinds, without limited thereto. Desirablyusable in the present invention among them, are diethylene glycoldimethyl ether, 1-ethoxy-2-propanol, propylene glycol monomethyl etheracetate, and mixed solvents of them, since they are most excellent insolubility for the acid generator in the resist components.

The usage amount of the organic solvent is preferably 200 to 5,000parts, and particularly 400 to 3,600 parts relative to 100 parts of baseresin.

While the amine compound or amine oxide compound having a carboxyl groupand having no hydrogen atoms covalently bonded to a nitrogen atom as abasic center of the present invention, is used in a manner blended in aresist composition as described above, the chemically amplified resistcomposition may be either positive or negative, and the chemicallyamplified positive material typically contains, in addition to thesolvent,

-   -   (A1) a base resin insoluble or hardly soluble in alkali, having        an acidic functional group protected by an acid labile group,        wherein the resin is made to be soluble in alkali when the acid        labile group is eliminated;    -   (B) an acid generator; and    -   (C) an amine compound or amine oxide compound having a carboxyl        group and having no hydrogen atoms covalently bonded to a        nitrogen atom as a basic center (where the nitrogen atom of the        amine is not included in an aromatic ring structure); or a        mixture of an amine compound or amine oxide compound having a        carboxyl group and having no hydrogen atoms covalently bonded to        a nitrogen atom as a basic center, with a basic compound        containing no carboxyl groups.

Numerously known as the base polymer (base resin) as the component (A-1)used for the chemically amplified positive resist of the presentinvention, are:

-   -   polyhydroxystyrene (PHS), and copolymer of PHS with styrene,        (meth)acrylic acid ester and another polymeric olefin compound,        in case of a resist for KrF excimer laser, or a resist for        electron beam (Japanese Patent Application Laid-open (kokai) No        2005-326833);    -   (meth)acrylic acid ester polymers, alternating copolymers of        cyclo-olefin and maleic anhydride, and copolymers including        vinyl ethers or (meth)acrylic acid ester (for example, Japanese        Patent Application Laid-open (kokai) No 2008-111103),        polynorbornene polymers, cyclo-olefin ring-opening metathesis        polymers, in case of a resist for ArF excimer laser;    -   fluorine-substituted products of the above polymers for KrF,        ArF, ring-closing polymerization based polymers using        fluorinated dienes, and the like, in case of a resist for F₂        laser; and    -   silicon-substituted products of the above polymers,        polysilsesquioxane polymers, and the like, in case of a        double-layered resist; and    -   any one of the above polymers is usable, without limited to the        polymerized polymers.

The base polymer can be used solely, or mixedly in two or more kinds. Incase of a positive resist, it is typical to decrease a dissolution rateof an unexposed area, by substituting a hydroxyl group of phenol,carboxyl group, or fluorinated alkyl alcohol, with an acid labile group.

Although the acid labile groups of the base polymer can be variouslyselected, the acid labile groups are preferably and exemplarily acetalgroups having 2 to 30 carbon atoms, tertiary alkyl groups having 4 to 30carbon atoms, particularly represented by the following formulae (P1)and (P2), respectively:

In the formulae (P1) and (P2), R¹¹ and R¹² are each a hydrogen atom, ora linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms,particularly 1 to 12 carbon atoms, which may contain a heteroatom suchas oxygen, sulfur, nitrogen, fluorine, or the like; and R¹³, R¹⁴, R¹⁵,and R¹⁶ are each a linear, branched, or cyclic alkyl group, aryl group,or aralkyl group having 1 to 20 carbon atoms, particularly 1 to 12carbon atoms, which may contain a heteroatom such as oxygen, sulfur,nitrogen, fluorine, or the like. Further, R¹¹ and R¹², R¹¹ and R¹³, R¹²and R¹³, R¹⁴ and R¹⁵, R¹⁴ and R¹⁶, and R¹⁵ and R¹⁶ may be bonded to eachother, to thereby form a ring having 3 to 20 carbon atoms, particularly3 to 12 carbon atoms, together with the carbon atom and oxygen atom, ifany, to which the applicable groups are bonded.

Examples of the acetal group represented by the formula (P1) concretelyinclude: a methoxymethyl group, ethoxymethyl group, propoxymethyl group,butoxymethyl group, isopropoxymethyl group, t-butoxymethyl group,1-methoxyethyl group, 1-methoxypropyl group, 1-methoxybutyl group,1-ethoxyethyl group, 1-ethoxypropyl group, 1-ethoxybutyl group,1-propoxyethyl group, 1-propoxypropyl group, 1-propoxybutyl group,1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group,2-methoxyisopropyl group, 2-ethoxyisopropyl group, 1-phenoxyethyl group,1-benzyloxyethyl group, 1-phenoxypropyl group, 1-benzyloxypropyl group,1-adamantyloxyethyl group, 1-adamantyloxypropyl group, 2-tetrahydrofurylgroup, 2-tetrahydro-2H-pyranyl group,142-cyclohexanecarbonyloxyethoxy)ethyl group,1-(2-cyclohexanecarbonyloxyethoxy)propyl group,1-[2-(1-adamantylcarbonyloxy)ethoxy]ethyl group, and1-[2-(1-adamantylcarbonyloxy)ethoxy]propyl group, without limitedthereto.

Examples of the tertiary alkyl group represented by the formula (P2)concretely include: t-butyl group, t-pentyl group,1-ethyl-1-methylpropyl group, 1,1-diethylpropyl group,1,1,2-trimethylpropyl group, 1-adamantyl-1-methylethyl group,1-methyl-1-(2-norbornyl)ethyl group,1-methyl-1-(tetrahydrofuran-2-yl)ethyl group,1-methyl-1-(7-oxanorbornane-2-yl)ethyl group, 1-methylcyclopentyl group,1-ethylcyclopentyl group, 1-propylcyclopentyl group,1-cyclopentylcyclopentyl group, 1-cyclohexylcyclopentyl group,1-(2-tetrahydrofuryl)cyclopentyl group,1-(7-oxanorbornane-2-yl)cyclopentyl group, 1-methyleyclohexyl group,1-ethylcyclohexyl group, 1-cyclopentylcyclohexyl group,1-cyclohexylcyclohexyl group, 2-methyl-2-norbornyl group,2-ethyl-2-norbornyl group, 8-methyl-8-tricyclo[5.2.1.0^(2,6)]decylgroup, 8-ethyl-8-tricyclo[5.2.1.0^(2,6)]decyl group,3-methyl-3-tetracyclo[4.4.0.1^(2,5),1^(7,10)]dodecyl group,3-ethyl-3-tetracyclo[4.4.0.1^(2,5),1^(7,10)]dodecyl group,2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group,1-methyl-3-oxo-1-cyclohexyl group,1-methyl-1-(tetrahydrofuran-2-yl)ethyl group,5-hydroxy-2-methyl-2-adamantyl group, and 5-hydroxy-2-ethyl-2-adamantylgroup, without limited thereto.

Further, part of the hydroxyl group of the base resin may becross-linked in an intermolecular or intramolecular manner, by an acidlabile group represented by the general formula (P3a) or (P3b):

-   -   wherein R¹⁷ and R¹⁸ each represent a hydrogen atom, or a linear,        branched, or cyclic alkyl group having 1 to 8 carbon atoms;    -   R¹⁷ and R¹⁸ may be bonded to each other to form a ring together        with a carbon atom to which they are bonded; and in case of        formation of the ring, R¹⁷ and R¹⁸ each represent a linear or        branched alkylene group having 1 to 8 carbon atoms;    -   R¹⁹ is a linear, branched, or cyclic alkylene group having 1 to        10 carbon atoms, and b is 0 or an integer of 1 to 10;    -   A represents a chain or alicyclic saturated hydrocarbon group,        aromatic hydrocarbon group, or heterocycle group having a        valence of a+1 and having 1 to 50 carbon atoms, and the group        may have an interposed heteroatom or may have some of hydrogen        atoms each substituted by a hydroxyl group, carboxyl group,        carbonyl group, or fluorine atom;    -   B represents —CO—O—, —NHCO—O—, or —NHCONH—; and    -   a is an integer of 1 to 7.

Examples of the cross-linked acetal represented by the general formula(P3a) or (P3b) concretely include those represented by the followingformulae (P3)-1 to (P3)-8, without limited thereto:

The base polymer preferably has a weight-average molecular weight of2,000 to 100,000 as determined relative to polystyrene standards by gelpermeation chromatography (GPC), and weight-average molecular weightsless than 2,000 may lead to deteriorated film-forming ability anddeteriorated resolution, while weight-average molecular weightsexceeding 100,000 may lead to deteriorated resolution or lead tooccurrence of extraneous substance upon formation of pattern.

Examples of the base polymer as the component (A-2) used for thechemically amplified negative resist of the present invention, include:

-   -   polyhydroxystyrene (PHS), and copolymer of PHS with styrene,        (meth)acrylic acid ester and another polymeric olefin compound,        in case of a resist for KrF excimer laser, or a resist for        electron beam;    -   (meth)acrylic acid ester polymers, alternating copolymers of        cyclo-olefin and maleic anhydride, and copolymers including        vinyl ethers or (meth)acrylic acid ester, polynorbornene        polymers, cyclo-olefin ring-opening metathesis polymers, in case        of a resist for ArF excimer laser;    -   fluorine-substituted products of the above polymers for KrF,        ArF, ring-closing polymerization based polymers using        fluorinated dienes, and the like, in case of a resist for F₂        laser; and    -   silicon-substituted products of the above polymers,        polysilsesquioxane polymers, and the like, in case of a        double-layered resist;    -   without limited to the polymerized polymers.

The base polymer can be used solely, or mixedly in two or more kinds. Incase of a negative resist, it is typical:

-   -   to obtain a solubility in alkali, by adopting a hydroxyl group        of phenol, carboxyl group, or fluorinated alkyl alcohol; and    -   to decrease a dissolution rate of an exposed portion, by        achieving polymer cross-linking upon generation of acids, by        means of a unit having a substitutional group such as epoxy        group or acetal group capable of forming a bond to another unit        in an electrophilic manner within the polymer, or by means of a        crosslinking agent.

Desirably usable examples (see Japanese Patent Application Laid-open(kokai) No 2006-201532) of the base polymer to be used for KrF excimerlaser or electron beam are represented as follows:

In case of these examples, solubility in alkali is obtained by acidityof phenolic hydroxyl group(s), and for example, adoption of a glycidylgroup as X allows for provision of a cross-linking reactivity betweenpolymers in the presence of acid catalyst. Further, the unit forproviding a cross-linking reactivity may be provided by copolymerizingwhat is possessed by an ester group of acrylic ester. Moreover, in caseof using an alkali-soluble base resin in combination with a crosslinkingagent, it is unnecessary to make the base polymer to have anelectrophilic reactivity.

Usable as a crosslinking agent to be blended in the chemically amplifiednegative resist are any ones insofar as configured to attainintramolecular and intermolecular cross-linking of the alkali-solublebase polymer, based on acids generated by a photoacid generator.Examples of preferable crosslinking agents includealkoxymethylglycolurils, and alkoxymethyl melamines.

Examples of desirable alkoxymethyl melamines include hexamethoxymethylmelamine and hexaethoxymethyl melamine.

Included as the component (B) of the chemically amplified resistcomposition of the present invention, is an acid generator, i.e., aso-called photoacid generator, as a neutral substance configured to bedecomposed by high energy radiation to thereby turn into an acidicsubstance. Those are called photoacid generators, respectively, hereinwhich generate acids by general high energy radiations without limitedto light, and this is to distinguish them from a thermal acid generatorto be used for thermosetting resins and the like. Usable as componentsof photoacid generators are basically any compounds insofar asconfigured to generate acids by irradiation of high energy radiation.Examples of typically used photoacid generators include sulfonium salts,iodonium salts, sulfonyldiazomethanes, N-sulfonyloxydicarboxylmides,O-arylsulfonyloximes, and O-alkylsulfonyloximes. Although preferableones are detailedly explained below, they may be used solely or mixedlyin two or more kinds.

Sulfonium salts are salts of sulfonium cations with sulfonates,bis(substituted alkylsulfonyl)imides, or tris(substitutedalkylsulfonyl)methides;

-   -   examples of sulfonium cations include: triphenylsulfonium,        (4-tert-butoxyphenyl)diphenylsulfonium,        bis(4-tert-butoxyphenyl)phenylsulfonium,        tris(4-tert-butoxyphenyl)sulfonium,        (3-tert-butoxyphenyl)diphenylsulfonium,        bis(3-tert-butoxyphenyl)phenylsulfonium,        tris(3-tert-butoxyphenyl)sulfonium,        (3,4-di-tert-butoxyphenyl)diphenylsulfonium,        bis(3,4-di-tert-butoxyphenyl)phenylsulfonium,        tris(3,4-di-tert-butoxyphenyl)sulfonium,        diphenyl(4-thiophenoxyphenyl)sulfonium,        (4-tert-butoxycarbonylmethyloxyphenyl)diphenylsulfonium,        tris(4-tert-butoxycarbonylmethyloxyphenyl)sulfonium,        (4-tert-butoxyphenyl)bis(4-dimethylaminophenyl)sulfonium,        tris(4-dimethylaminophenyl)sulfonium,        4-methylphenyldiphenylsulfonium,        4-tert-butylphenyldiphenylsulfonium,        bis(4-methylphenyl)phenylsulfonium,        bis(4-tert-butylphenyl)phenylsulfonium,        tris(4-methylphenyl)sulfonium,        tris(4-tert-butylphenyl)sulfonium, tris(phenylmethyl)sulfonium,        2-naphthyldiphenylsulfonium, dimethyl-2-naphthylsulfonium,        4-hydroxyphenyldimethylsulfonium,        4-methoxyphenyldimethylsulfonium, trimethylsulfonium,        2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium,        tribenzylsulfonium, diphenylmethylsulfonium,        dimethylphenylsulfonium, 2-oxopropylthiacyclopentanium,        2-oxobutylthiacyclopentanium,        2-oxo-3,3-dimethylbutylthiacyclopentanium,        2-oxo-2-phenylethylthiacyclopentanium,        4-n-butoxynaphthyl-1-thiacyclopentanium, and        2-n-butoxynaphthyl-1-thiacyclopentanium;    -   examples of sulfonates include: trifluoromethanesulfonate,        pentafluoroethanesulfonate, heptafluoropropanesulfonate,        nonafluorobutanesulfonate, tridecafluorohexanesulfonate,        perfluoro(4-ethylcyclohexane)sulfonate,        heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,        pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate,        4-fluorobenzenesulfonate, mesitylenesulfonate,        2,4,6-triisopropylbenzenesulfonate, toluenesulfonate,        benzenesulfonate, 4-(p-toluenesulfonyloxy)benzenesulfonate,        6-(p-toluenesulfonyloxy)naphthalene-2-sulfonate,        4-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,        5-(p-toluenesulfonyloxy)naphthalene-1-sultanate,        8-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,        naphthalenesulfonate, camphorsulfonate, octanesulfonate,        dodecylbenzenesulfonate, butanesulfonate, methanesulfonate,        1,1-difluoro-2-naphthylethanesulfonate,        1,1,2,2-tetrafluoro-2-(norbornan-2-yl)ethanesulfonate,        1,1,2,2-tetrafluoro-2-(tetracyclo[4.4.0.1^(2,5),1^(7,10)]dodec-3-en-8-yl)ethanesulfonate,        2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,        1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,        2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,        2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,        1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,        1,1-difluoro-2-tosyloxyethanesulfonate,        adamantanemethoxycarbonyldifluoromethanesulfonate,        1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate,        methoxycarbonyldifluoromethanesulfonate,        1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yl-oxycarbonyl)difluoromethanesulfonate,        and 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate;    -   examples of bis(substituted alkylsulfonyl)imides include:        bis(trifluoromethylsulfonyl)imide,        bis(pentafluoroethylsulfonyl)imide,        bis(heptafluoropropylsulfonyl)imide, and        perfluoro(1,3-propylenebissulfonyl)imide;    -   examples of tris(substituted alkylsulfonyl)methide include        tris(trifluoromethylsulfonyl)methide; and    -   examples of sulfonium salts include combinations of the above.

Iodonium salts are salts of iodonium cations with sulfonates,bis(substituted alkylsulfonyl)imides, or tris(substitutedalkylsulfonyl)methides;

-   -   examples of iodonium cations include: aryliodonium cations        including diphenyliodinium, bis(4-tert-butylphenyl)iodonium,        4-tert-butoxyphenylphenyliodonium, and        4-methoxyphenylphenyliodonium;    -   examples of sulfonates include: trifluoromethanesulfonate,        pentafluoroethanesulfonate, heptafluoropropanesulfonate,        nonafluorobutanesulfonate, tridecafluorohexanesulfonate,        perfluoro(4-ethylcyclohexane)sulfonate,        heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,        pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate,        4-fluorobenzenesulfonate, mesitylenesulfonate,        2,4,6-triisopropylbenzenesulfonate, toluenesulfonate,        benzenesulfonate, 4-(p-toluenesulfonyloxy)benzenesulfonate,        6-(p-toluenesulfonyloxy)naphthalene-2-sulfonate,        4-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,        5-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,        8-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,        naphthalenesulfonate, eamphorsulfonate, octanesulfonate,        dodecylbenzenesulfonate, butanesulfonate, methanesulfonate,        1,1-difluoro-2-naphthyl-ethanesulfonate,        1,1,2,2-tetrafluoro-2-(norbornan-2-yl)ethanesulfonate,        1,1,2,2-tetrafluoro-2-(tetracyclo[4.4.0.1^(2,5),1^(7,10)]dodec-3-en-8-yl)ethanesulfonate,        2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,        1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,        2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,        2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,        1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,        1,1-difluoro-2-tosyloxyethanesulfonate,        adamantanemethoxycarbonyldifluoromethanesulfonate,        1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate,        methoxycarbonyldifluoromethanesulfonate,        1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yl-oxycarbonyl)difluoromethanesulfonate,        and 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate;    -   examples of bis(substituted alkylsulfonyl)imides include:        bis(trifluoromethylsulfonyl)imide,        bis(pentafluoroethylsulfonyl)imide,        bis(heptafluoropropylsulfonyl)imide, and        perfluoro(1,3-propylenebissulfonyl)imide;    -   examples of tris(substituted alkylsulfonyl)methide include        tris(trifluoromethylsulfonyl)methide; and    -   examples of iodonium salts include combinations of the above.

Examples of sulfonyldiazomethanes include bissulfonyl-diazomethanes andsulfonyl-carbonyldiazomethanes such as: bis(ethylsulfonyl)diazomethane,bis(1-methylpropylsulfonyl)diazomethane,bis(2-methylpropylsulfonyl)diazomethane,bis(1,1-dimethylethylsulfonyl)diazomethane,bis(cyclohexylsulfonyl)diazomethane,bis(perfluoroisopropylsulfonyl)diazomethane,bis(phenylsulfonyl)diazomethane,bis(4-methylphenylsulfonyl)diazomethane,bis(2,4-dimethylphenylsulfonyl)diazomethane,bis(4-acetyloxyphenylsulfonyl)diazomethane,bis(4-methanesulfonyloxyphenylsulfonyl)diazomethane,bis(4-(p-toluenesulfonyloxy)phenylsulfonyl)diazomethane,bis(4-n-hexyloxyphenylsulfonyl)diazomethane,bis(2-methyl-4-n-hexyloxyphenylsulfonyl)diazomethane,bis(2,5-dimethyl-4-n-hexyloxyphenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-n-hexyloxyphenylsulfonyl)diazomethane,bis(2-methyl-5-isopropyl-4-n-hexyloxyphenylsulfonyl)diazomethane,bis(2-naphthylsulfonyl)diazomethane,4-methylphenylsulfonylbenzoyldiazomethane,tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane,2-naphthylsulfonylbenzoyldiazomethane,4-methylphenylsulfonyl-2-naphthoyldiazomethane,methylsulfonylbenzoyldiazomethane, andtert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane.

Examples of N-sulfonyloxydicarboxylmide type photoacid generatorsinclude compounds, which are combinations of:

-   -   imide structures such as: succinimide, naphthalenedicarboximide,        phthalimide, cyclohexyldicarboximide,        5-norbornene-2,3-dicarboximide, and        7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboximide;    -   with: trifluoromethanesulfonate, pentafluoroethanesulfonate,        heptafluoropropanesulfonate, nonafluorobutanesulfonate,        tridecafluorohexanesulfonate,        perfluoro(4-ethylcyclohexane)sulfonate,        heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,        pentafluorobenzenesulfonate,        4-(trifluoromethyl)benzenesulfonate, 4-fluorobenzenesulfonate,        mesitylenesulfonate, 2,4,6-triisopropylbenzenesulfonate,        toluenesulfonate, benzenesulfonate,        4-(p-toluenesulfonyloxy)benzenesulfonate,        6-(p-toluenesulfonyloxy)naphthalene-2-sulfonate,        4-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,        5-(p-toluenesulfonyloxy)naphtlialene-1-sulfonate,        8-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,        naphthalenesulfonate, camphorsulfonate, octanesulfonate,        dodecylbenzenesulfonate, butanesulfonate, methanesulfonate,        1,1-difluoro-2-naphthylethanesulfonate,        1,1,2,2-tetrafluoro-2-(norbornan-2-yl)ethanesulfonate,        1,1,2,2-tetrafluoro-2-(tetracyclo[4.4.0.1^(2,5)1^(7,10)]dodec-3-en-8-yl)ethanesulfonate,        2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,        1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,        2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,        2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,        1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,        1,1-difluoro-2-tosyloxyethanesulfonate,        adamantanemethoxycarbonyldifluoromethanesulfonate,        1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate,        methoxycarbonyldifluoromethanesulfonate,        1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yl-oxycarbonyl)difluoromethanesulfonate,        and 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.

Examples of O-arylsulfonyloxime compounds or O-alkylsulfonyloximecompound (oxime sulfonate) type photoacid generators include: glyoximederivative types; oxime sulfonate types each with a long conjugatedsystem including intervening thiophene or cyclohexadiene; oximesulfonate types having an electron withdrawing group such astrifluoromethyl group for increasing a stability of the compound; oximesulfonate types using phenylacetonitrile or substituted acetonitrilederivatives; and bisoxime sulfonate types.

Examples of glyoxime derivative type photoacid generators include:bis-β-(p-toluenesulfonyl)-α-dimethylglyoxime,bis-O-(p-toluenesulfonyl)-α-diphenylglyoxime,bis-O-(p-toluenesulfonyl)-α-dicyclohexylglyoxime,bis-O-(p-toluenesulfonyl)-2,3-pentanedionedioxime,bis-O-(n-butanesulfonyl)-α-dimethylglyoxime,bis-O-(n-butanesulfonyl)-α-diphenylglyoxime,bis-O-(n-butanesulfonyl)-α-dicyclohexylglyoxime,bis-O-(methanesulfonyl)-α-dimethylglyoxime,bis-O-(trifluoromethanesulfonyl)-α-dimethylglyoxime,bis-O-(2,2,2-trifluoroethanesulfonyl)-α-dimethylglyoxime,bis-O-(10-camphorsulfonyl)-α-dimethylglyoxime,bis-O-(benzenesulfonyl)-α-dimethylglyoxime,bis-β-(4-fluorobenzenesulfonyl)-α-dimethylglyoxime,bis-O-(4-trifluoromethylbenzenesulfonyl)-α-dimethylglyoxime,bis-O-(xylenesulfonyl)-α-dimethylglyoxime,bis-O-(trifluoromethanesulfonyl)-nioxime,bis-O-(2,2,2-trifluoroethanesulfonyl)-nioxime,bis-O-(10-camphorsulfonyl)-nioxime, bis-O-(benzenesulfonyl)-nioxime,bis-O-(4-fluorobenzenesulfonyl)-nioxime,bis-O-(4-trifluoromethylbenzenesulfonyl)-nioxime, andbis-O-(xylenesulfonyl)-nioxime; and

-   -   compounds of the above structures substituted by:        2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,        1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,        2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,        2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,        1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,        1,1-difluoro-2-tosyloxyethanesulfonate,        adamantanemethoxycarbonyldifluoromethanesulfonate,        1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate,        methoxycarbonyldifluoromethanesulfonate,        1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yl-oxycarbonyl)difluoromethanesulfonate,        and 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.

Examples of oxime sulfonate type photoacid generators each with a longconjugated system including intervening thiophene or cyclohexadiene,include:

-   -   (5-(p-toluenesulfonyl)oxyimino-5H-thiophen-2-ylidene)phenylacetonitrile,        (5-(10-camphorsulfonyl)oxyimino-5H-thiophen-2-ylidene)phenylacetonitrile,        (5-n-octanesulfonyloxylmino-5H-thiophen-2-ylidene)phenylacetonitrile,        (5-(p-toluenesulfonyl)oxyimino-5H-thiophen-2-ylidene)(2-methylphenyl)acetonitrile,        (5-(10-camphorsulfonyl)oxyimino-5H-thiophen-2-ylidene)(2-methylphenyl)acetonitrile,        (5-n-octanesulfonyloxyimino-5H-thiophen-2-ylidene)(2-methylphenyl)acetonitrile,        (5-(4-(p-toluenesulfonyloxy)benzenesulfonyl)oxyimino-5H-thiophen-2-ylidene)phenylacetonitrile,        and        (5-(2,5-bis(p-toluenesulfonyloxy)benzenesulfonyl)oxyimino-5H-thiophen-2-ylidene)phenylacetonitrile;        and    -   compounds of the above structures substituted by:        2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,        1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,        2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,        2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,        1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,        1,1-difluoro-2-tosyloxyethanesulfonate,        adamantanemethoxycarbonyldifluoromethanesulfonate,        1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate,        methoxycarbonyldifluoromethanesulfonate,        1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxycarbonyl)difluoromethanesulfonate,        and 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.

Examples of oxime sulfonate type photoacid generators having an electronwithdrawing group such as trifluoromethyl group for increasing astability of the compound, include:

-   -   2,2,2-trifluoro-1-phenyl-ethanone═O-(methylsulfonyl)oxime,    -   2,2,2-trifluoro-1-phenyl-ethanone═O-(10-camphorsulfonyl)oxime,    -   2,2,2-trifluoro-1-phenylethanone═O-(4-methoxybenzenesulfonyl)oxime,    -   2,2,2-trifluoro-1-phenylethanone═O-(1-naphthylsulfonyl)oxime,    -   2,2,2-trifluoro-1-phenylethanone═O-(2-naphthylsulfonyl)oxime,    -   2,2,2-trifluoro-1-phenylethanone═O-(2,4,6-trimethylphenylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-methylphenyl)ethanone═O-(10-camphorsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-methylphenyl)ethanone═O-(methylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(2-methylphenyl)ethanone═O-(10-camphorsulfonyl)oxime,    -   2,2,2-trifluoro-1-(2,4-dimethylphenyl)ethanone═O-(10-camphorsulfonyl)oxime,    -   2,2,2-trifluoro-1-(2,4-dimethylphenyl)ethanone═O-(1-naphthyl        sulfonyl)oxime,    -   2,2,2-trifluoro-1-(2,4-dimethylphenyl)-ethanone═O-(2-naphthylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)ethanone═O-(10-camphorsulfonyl)oxime,    -   2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)ethanone═O-(1-naphthylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)ethanone═O-(2-naphthylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-methoxyphenyl)ethanone═O-(methylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-methylthiophenyl)-ethanone═O-(methylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(3,4-dimethoxyphenyl)ethanone═O-(methylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-methoxyphenyl)ethanone═O-(4-methylphenylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-methoxyphenyl)ethanone═O-(4-methoxyphenylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-methoxyphenyl)ethanone═O-(4-dodecylphenylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-methoxyphenyl)ethanone-O-(octylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-thiomethylphenyl)ethanone═O-(4-methoxyphenylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-thiomethylphenyl)ethanone═O-(4-dodecylphenylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-thiomethylphenyl)ethanone═O-(octylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-thiomethylphenyl)ethanone═O-(2-naphthylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(2-methylphenyl)ethanone═O-(methylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-methylphenyl)ethanone═O-(phenylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-chlorophenyl)ethanone═O-(phenylsulfonyl)oxime,    -   2,2,3,3,4,4,4-heptafluoro-1-phenylbutanone═O-(10-camphorsulfonyl)oxime,    -   2,2,2-trifluoro-1-(1-naphthyl)ethanone-O-(methylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(2-naphthyl)ethanone═O-(methylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-benzylphenyl)ethanone═O-(methylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-(phenyl-1,4-dioxa-but-1-yl)phenyl)ethanone═O-(methylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(1-naphthyl)ethanone═O-(propylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(2-naphthyl)ethanone═O-(propylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-benzylphenyl)ethanone═O-(propylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-methylsulfonylphenyl)ethanone═O-(propylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-methylsulfonyloxyphenyl)ethanone-O-(propylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-methylcarbonyloxyphenyl)ethanone═O-(propylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(61-1,7H-5,8-dioxonaphth-2-yl)ethanone═O-(propylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-methoxycarbonyl)ethoxyphenyl)ethanone═O-(propylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-methoxycarbonyl)-(4-amino-1-oxa-pent-1-yl)phenyl)ethanone═O-(propylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(3,5-dimethyl-4-ethoxyphenyl)ethanone═O-(propylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-benzyloxyphenyl)ethanone═O-(propylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(2-thiophenyl)ethanone═O-(propylsulfonate)oxime,    -   2,2,2-trifluoro-1-(1-dioxathiophen-2-yl)ethanone═O-(propylsulfonate)oxime;        2,2,2-trifluoro-1-(4-(3-(4-(2,2,2-trifluoro-1-(trifluoromethanesulfonyloxylmino)ethyl)phenoxy)propoxy)phenyl)ethanone═O-(trifluoromethanesulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-(3-(4-(2,2,2-trifluoro-1-(1-propanesulfonyloxyimino)ethyl)phenoxy)propoxy)phenyl)ethanone═O-(propylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-(3-(4-(2        fluoro-1-(1-butanesulfonyloxyimino)ethyl)phenoxy)propoxy)phenyl)ethanone═O-(butylsulfonyl)oxime,    -   2,2,2-trifluoro-1-(4-(3-(4-(2,2,2-trifluoro-1-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxylmino)ethyl)phenoxy)propoxy)phenyl)ethanone═O-(4-(4-methylphenylsulfonyloxy)phenylsulfonyl)oxime,        and    -   2,2,2-trifluoro-1-(4-(3-(4-(2,2,2-trifluoro-1-(2,5-bis(4-methylphenylsulfonyloxy)benzenesulfonyloxy)phenylsulfonyloxyimino)ethyl)phenoxy)propoxy)phenyl)ethanone═O-(2,5-bis(4-methylphenylsulfonyloxy)benzenesulfonyloxy)phenylsulfonyl)oxime;        and    -   compounds of the above structures substituted by:        2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,        1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,        2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,        2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,        1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,        1,1-difluoro-2-tosyloxyethanesulfonate,        adamantanemethoxycarbonyldifluoromethanesulfonate,        1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate,        methoxycarbonyldifluoromethanesulfonate,        1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxycarbonyl)difluoromethanesulfonate,        and 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.

Examples of the photoacid generators noted just above further includeoxime sulfonates represented by the following formula (Ox-1):

-   -   wherein R⁴⁰¹ represents a substituted or unsubstituted        haloalkylsulfonyl group or halobenzenesulfonyl group having 1 to        10 carbon atoms;    -   R⁴⁰² represents a haloalkyl group having 1 to 11 carbon atoms;        and    -   Ar⁴⁰¹ represents a substituted or unsubstituted aromatic group        or heteroaromatic group.

Examples of the photoacid generators concretely include:

-   -   2-(2,2,3,3,4,4,5,5-octafluoro-1-(nonafluorobutylsulfonyloxyimino)pentyl)fluorene,        2-(2,2,3,3,4,4-pentafluoro-1-(nonafluorobutylsulfonyloxyimino)butyl)fluorene,        2-(2,2,3,3,4,4,5,5,6,6-decafluoro-1-(nonafluorobutylsulfonyloxyimino)hexyl)fluorene,        2-(2,2,3,3,4,4,5,5-octafluoro-1-(nonafluorobutylsulfonyloxyimino)pentyl)-4-biphenyl,        2-(2,2,3,3,4,4-pentafluoro-1-(nonafluorobutylsulfonyloxyimino)butyl)-4-biphenyl,        and        2-(2,2,3,3,4,4,5,5,6,6-decafluoro-1-(nonafluorobutylsulfonyloxyimino)hexyl)-4-biphenyl;        and    -   compounds of the above structures substituted by:        2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,        1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,        2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,        2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,        1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,        1,1-difluoro-2-tosyloxyethanesulfonate,        adamantanemethoxycarbonyldifluoromethanesulfonate,        1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate,        methoxycarbonyldifluoromethanesulfonate,        1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxycarbonyl)difluoromethanesulfonate,        and 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.

Examples of the oxime sulfonate types using phenylacetonitrile orsubstituted acetonitrile derivatives, include:

-   -   α-(p-toluenesulfonyloxyimino)-phenylacetonitrile,        α-(p-chlorobenzenesulfonyloxyimino)-phenylacetonitrile,        α-(4-nitrobenzenesulfonyloxyimino)-phenyl acetonitrile,        α-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimino)phenylacetonitrile,        α-(benzenesulfonyloxyimino)-4-chlorophenylacetonitrile,        α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile,        α-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile,        α-(benzenesulfonyloxyimino)-4-methoxyphenylacetonitrile,        α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitile,        α-(benzenesulfonyloxyimino)-2-thienylacetonitrile,        α-(4-dodecylbenzenesulfonyloxyimino)-phenylacetonitrile,        α-[(4-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile,        α-[(dodecylbenzenesulfonyloxylmino)-4-methoxyphenyl]acetonitrile,        α-(tosyloxyimino)-3-thienylacetonitrile,        α-(methylsulfonyloxylmino)-1-cyclopentenylacetonitrile,        α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile,        α-(isopropylsulfonyloxylmino)-1-cyclopentenylacetonitrile,        α-(n-butylsulfonyloxyimino)-1-cyclopentenylacetonitrile,        α-(ethylsulfonyloxyimino)-1-cyclohexenylacetonitrile,        α-(isopropylsulfonyloxyimino)-1-cyclohexenylacetonitrile, and        α-(n-butylsulfonyloxyimino)-1-cyclohexenylacetonitrile; and    -   compounds of the above structures substituted by:        2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,        1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,        2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,        2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,        1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,        1,1-difluoro-2-tosyloxyethanesulfonate,        adamantanemethoxycarbonyldifluoromethanesulfonate,        1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate,        methoxycarbonyldifluoromethanesulfonate,        1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxycarbonyl)difluoromethanesulfonate,        and 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.

Further, examples of the bisoxime sulfonate types include:

-   -   bis(α-(p-toluenesulfonyloxy)imino)-p-phenylenediacetonitrile,        bis(α-(benzenesulfonyloxy)imino)-p-phenylenediacetonitrile,        bis(α-(methanesulfonyloxy)imino)-p-phenylenediacetonitrile,        bis(α-(butanesulfonyloxy)imino)-p-phenylenediacetonitrile,        bis(α-(10-camphorsulfonyloxy)imino)-p-phenylenediacetonitrile,        bis(α-(trifluoromethanesulfonyloxy)imino)-p-phenylenediacetonitrile,        bis(α-(4-methoxybenzenesulfonyloxy)imino)-p-phenylenediacetonitrile,        bis(α-(p-toluenesulfonyloxy)imino)-m-phenylenediacetonitrile,        bis(α-(benzenesulfonyloxy)imino)-m-phenylenediacetonitrile,        bis(α-(methanesulfonyloxy)imino)-m-phenylenediacetonitrile,        bis(α-(butanesulfonyloxy)imino)-m-phenylenediacetonitrile,        bis(α-(10-camphorsulfonyloxy)imino)-m-phenylenediacetonitrile,        bis(α-(trifluoromethanesulfonyloxy)imino)-m-phenylenediacetonitrile,        and        bis(α-(4-methoxybenzenesulfonyloxy)imino)-m-phenylenediacetonitrile;        and    -   compounds of the above structures substituted by:        2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,        1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,        2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,        2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,        1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,        1,1-difluoro-2-tosyloxyethanesulfonate,        adamantanemethoxycarbonyldifluoromethanesulfonate,        1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate,        methoxycarbonyldifluoromethanesulfonate,        1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxycarbonyl)difluoromethanesulfonate,        and 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.

Among the above photoacid generators, examples to be obtained withdesirable sensitivity and stability, include sulfonium salts,bissulfonyl-diazomethanes, N-sulfonyloxyimides, and oxime-O-sulfonates.

Among the above, more preferable examples of sulfonium salts include:

-   -   triphenylsulfonium p-toluenesulfonate, triphenylsulfonium        camphorsulfonate, triphenylsulfonium        pentafluorobenzenesulfonate, triphenylsulfonium        nonafluorobutanesulfonate, triphenylsulfonium        4-(p-toluenesulfonyloxy)benzenesulfonate, triphenylsulfonium        2,4,6-triisopropylbenzenesulfonate,        4-tert-butoxyphenyldiphenylsulfonium p-toluenesulfonate,        4-tert-butoxyphenyldiphenylsulfonium camphorsulfonate,        4-tert-butoxyphenyldiphenylsulfonium        4-(p-toluenesulfonyloxy)benzenesulfonate,        4-tert-butylphenyldiphenylsulfonium camphorsulfonate,        4-tert-butylphenyldiphenylsulfonium        2,4,6-triisopropylbenzenesulfonate,        tris(4-methylphenyl)sulfonium camphorsulfonate,        tris(4-tert-butylphenyl)sulfonium camphorsulfonate,        10-phenylphenoxathiinium 2,4,6-triisopropylbenzenesulfonate,        triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium        pentafluoroethanesulfonate, triphenylsulfonium        heptafluoropropanesulfonate, triphenylsulfonium        nonafluorobutanesulfonate, triphenylsulfonium        tridecafluorohexanesulfonate, triphenylsulfonium        heptadecafluorooctanesulfonate, triphenylsulfonium        perfluoro(4-ethylcyclohexane)sulfonate,        4-methylphenyldiphenylsulfonium nonafluorobutanesulfonate,        2-oxo-2-phenylethylthiacyclopentanium nonafluorobutanesulfonate,        4-tert-butylphenyldiphenylsulfonium nonafluorobutanesulfonate,        4-tert-butylphenyldiphenylsulfonium        perfluoro(4-ethylcyclohexane)sulfonate,        4-tert-butylphenyldiphenylsulfonium heptafluorooctanesulfonate,        triphenylsulfonium 1,1-difluoro-2-naphthylethanesulfonate,        triphenylsulfonium        1,1,2,2-tetrafluoro-2-(norbornan-2-yl)ethanesulfonate,        triphenylsulfonium        2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        triphenylsulfonium        1,1,3,3,3-pentafluoro-2-(pivaloyloxy)propanesulfonate,        triphenylsulfonium        2-(cyclohexanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        triphenylsulfonium        2-(2-naphthoyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        triphenylsulfonium        2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        triphenylsulfonium        2-hydroxy-1,1,3,3,3-pentafluoropropanesulfonate,        triphenylsulfonium        adamantanemethoxycarbonyldifluoromethanesulfonate,        triphenylsulfonium        1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate,        triphenylsulfonium methoxycarbonyldifluoromethanesulfonate,        4-tert-butylphenyldiphenylsulfonium        2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        4-tert-butylphenyldiphenylsulfonium        1,1,3,3,3-pentafluoro-2-(pivaloyloxy)propanesulfonate,        4-tert-butylphenyldiphenylsulfonium        2-(cyclohexanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        4-tert-butylphenyldiphenylsulfonium        2-(2-naphthoyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        4-tert-butylphenyldiphenylsulfonium        2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,        4-tert-butylphenyldiphenylsulfonium        2-hydroxy-1,1,3,3,3-pentafluoropropanesulfonate,        4-tert-butylphenyldiphenylsulfonium        adamantanemethoxycarbonyldifluoromethanesulfonate,        4-tert-butylphenyldiphenylsulfonium        1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate,        and 4-tert-butylphenyldiphenylsulfonium        methoxycarbonyldifluoromethanesulfonate.

Examples of bissulfonyl-diazomethanes include:

-   -   bis(tert-butylsulfonyl)diazomethane,        bis(cyclohexylsulfonyl)diazomethane,        bis(2,4-dimethylphenylsulfonyl)diazomethane,        bis(4-n-hexyloxyphenylsulfonyl)diazomethane,        bis(2-methyl-4-n-hexyloxyphenylsulfonyl)diazomethane,        bis(2,5-dimethyl-4-n-hexyloxyphenylsulfonyl)diazomethane,        bis(3,5-dimethyl-4-n-hexyloxyphenylsulfonyediazornethane,        bis(2-methyl-5-isopropyl-4-n-hexyloxy)phenylsulfonyldiazomethane,        and bis(4-tert-butylphenylsulfonyl)diazomethane.

Further, examples of N-sulfonyloxyimides include:

-   -   N-camphorsulfonyloxy-5-norbornene-2,3-dicarboxylic acid imide,        N-p-toluenesulfonyloxy-5-norbornene-2,3-dicarboxylic acid imide,        (5-(10-camphorsulfonyl)oxyimino-5H-thiophen-2-ylidene)(2-methylphenyl)acetonitrile,        and        (5-(p-toluenesulfonyl)oxyimino-5H-thiophen-2-ylidene)(2-methylphenyl)acetonitrile.

Furthermore, examples of oxime-O-sulfonates include:

-   -   2-oxo-2-phenylethylthiacyclopentanium        2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        2-oxo-2-phenylethylthiacyclopentanium        2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,        triphenylsulfonium perfluoro(1,3-propylenebissulfonyl)imide,        triphenylsulfonium bis(pentafluoroethylsulfonyl)imide,        2-(2,2,3,3,4,4,5,5-octafluoro-1-(nonafluorobutylsulfonyloxyimino)pentyl)fluorene,        2-(2,2,3,3,4,4-pentafluoro-1-(nonafluorobutylsulfonyloxyimino)butyl)fluorene,        2-(2,2,3,3,4,4,5,5,6,6-decafluoro-1-(nonafluorobutylsulfonyloxyimino)hexyl)fluorene,        2-(2,2,3,3,4,4,5,5-octafluoro-1-(2-(cyclohexanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonyloxyimino)pentyl)fluorene,        2-(2,2,3,3,4,4-pentafluoro-1-(2-(cyclohexanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonyloxyimino)butyl)fluorene,        and        2-(2,2,3,3,4,4,5,5,6,6-decafluoro-1-(nonafluorobutylsulfonyloxyimino)hexyl)fluorene.

Although the addition amount of the photoacid generator in thechemically amplified resist composition of the present invention is notparticularly limited, the adding amount is to be 0.4 to 20 weight parts,preferably 0.8 to 15 weight parts relative to 100 weight parts of thebase resin (i.e., the component (A)) in the resist composition. Althoughsimultaneous increase of the photoacid generator addition amount and thebasic substance addition amount allows assurance of sensitivity anddecrease of line edge roughness to be expected, adding amounts of thephotoacid generator exceeding 20 weight parts typically lead todeteriorated sensitivity-improving effects and thus may be uneconomical.Further, adding amounts less than 0.4 weight parts necessitate todecrease the basic substance amount in order to meet the requiredsensitivity, thereby possibly increasing roughness of a formed resistpattern. Particularly, when the resist composition is used to form aresist film for irradiation of radiation or irradiation of electron beamthereto, addition of a photoacid generator is not problematic in energyattenuation of irradiated radiation within a film though highersensitivity is scarcely obtained then, so that the addition amount ofthe photoacid generator is made to be a higher concentration such aspreferably about 2.0 to 20 weight parts, as compared to a situation ofadoption of excimer laser light.

Although the amine compound or amine oxide compound having a carboxylgroup and having no hydrogen atoms covalently bonded to a nitrogen atomas a basic center as the basic component, which is the component (C) tobe blended in the chemically amplified resist composition of the presentinvention, may be used solely or combinedly with each other, it is alsopossible to use them combinedly with other basic compounds such ashaving no carboxyl groups, in view of the above mechanism assumed by thepresent inventors.

Examples of basic compounds having no carboxyl groups upon mixed usage,include any known nitrogen-containing organic compounds having beenconventionally used in resist compositions, particularly in chemicallyamplified resist compositions, and concretely include: primary,secondary, and tertiary aliphatic amines, mixed amines, aromatic amines,heterocyclic amines, nitrogen-containing compounds having sulfonylgroup, nitrogen-containing compounds having hydroxyl group,nitrogen-containing compounds having hydroxyphenyl group, alcoholicnitrogen-containing compounds, amides, imides, and carbamates.

Concretely, examples of primary aliphatic amines include: ammonia,methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,isobutylamine, sec-butylamine, tert-butylamine, pentylamine,tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine,heptylamine, octylamine, nonylamine, decylamine, dodecylamine,cetylamine, methylenediamine, ethylenediamine, andtetraethylenepentamine; examples of secondary aliphatic amines includedimethylamine, diethylamine, di-n-propylamine, diisopropylamine,di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine,dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine,dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine,N,N-dimethyl methylenediamine, N,N-dimethyl ethylenediamine, andN,N-dimethyl tetraethylenepentamine; and examples of tertiary aliphaticamines include trimethylamine, triethylamine, tri-n-propyl amine,triisopropylamine, tri-n-butylamine, triisobutylamine,tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine,tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine,tridecylamine, tridodecylamine, tricetylamine, N,N,N′,N′-tetramethylmethylenediamine, N,N,N′,N′-tetramethyl ethylenediamine, andN,N,N′,N′-tetramethyl tetraethylenepentamine.

Examples of mixed amines include dimethylethylamine,methylethylpropylamine, benzylamine, phenethylamine, andbenzyldimethylamine. Examples of aromatic amines and heterocyclic aminesinclude aniline derivatives (e.g., aniline, N-methylaniline,N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline,3-methylaniline, 4-methylaniline, ethylaniline, propylaniline,trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline,2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, andN,N-dimethyltoluidine), diphenyl(p-tolyl)amine, methyldiphenylamine,triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene,pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole,2,4-dimethylpyrrole, 2,5-dimethylpyrrole, and N-methylpyrrole), oxazolederivatives (e.g., oxazole and isooxazole), thiazole derivatives (e.g.,thiazole and isothiazole), imidazole derivatives (e.g., imidazole,4-methylimidazole, and 4-methyl-2-phenylimidazole), pyrazolederivatives, furazan derivatives, pyrroline derivatives (e.g., pyrrolineand 2-methyl-1-pyrroline), pyrrolidine derivatives (e.g., pyrrolidine,N-methylpyrrolidine, pyrrolidinone, and N-methylpyrrolidone),imidazoline derivatives, imidazolidine derivatives, pyridine derivatives(e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine,butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpridine,trimethylpyridine, triethylpyridine, phenylpyridine,3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine,benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine,4-pyrrolidinopyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, anddimethylaminopyridine), pyridazine derivatives, pyrimidine derivatives,pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives,piperidine derivatives, piperazine derivatives, morpholine derivatives,indole derivatives, isoindole derivatives, 1H-indazole derivatives,indoline derivatives, quinoline derivatives (e.g., quinoline and3-quinolinecarbonitrile), isoquinoline derivatives, cinnolinederivatives, quinazoline derivatives, quinoxaline derivatives,phthalazine derivatives, purine derivatives, pteridine derivatives,carbazole derivatives, phenanthridine derivatives, acridine derivatives,phenazine derivatives, 1,10-phenanthroline derivatives, adeninederivatives, adenosine derivatives, guanine derivatives, guanosinederivatives, uracil derivatives, and uridine derivatives.

Examples of nitrogen-containing compounds having sulfonyl group include3-pyridinesulfonic acid, pyridinium p-toluenesulfonate;

-   -   examples of nitrogen-containing compounds having hydroxyl group,        nitrogen-containing compounds having hydroxyphenyl group, and        alcoholic nitrogen-containing compounds include:        2-hydroxypyridine, aminocresol, 2,4-quinolinediol,        3-indolemethanol hydrate, monoethanolamine, diethanolamine,        triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine,        triisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol,        3-amino-1-propanol, 4-amino-1-butanol,        4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine,        1-(2-hydroxyethyl)piperazine,        1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidine ethanol,        1-(2-hydroxyethyl)pyrrolidine,        1-(2-hydroxyethyl)-2-pyrrolidinone,        3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol,        8-hydroxyjulolidine, 3-quinuclidinol, 3-tropanol,        1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol,        N-(2-hydroxyethyl)phthalimide, and        N-(2-hydroxyethyl)isonicotinamide. Examples of amides include        formamide, N-methylformamide, N,N-dimethylformamide, acetamide,        N-methylacetamide, N,N-dimethylacetamide, propionamide,        benzamide, and 1-cyclohexylpyrrolidone. Examples of imides        include phthalimide, succinimide, and maleimide. Examples of        carbamates include N-tert-butoxycarbonyl-N,N-dicyclohexylamine,        N-tert-butoxycarbonylbenzimidazole, and oxazolidinone.

Further exemplified are the following nitrogen-containing organiccompounds represented by the following general formula (B)-1:N(X′)_(n)(Y)_(3-n)  (B)-1

-   -   wherein, n=1, 2, or 3;    -   the side-chains X′ may be the same or different, and can be        represented by the following general formulae (X′1) to (X′3):

-   -   wherein, the side-chain(s), Y represents a hydrogen atom, or the        same or different linear, branched, or cyclic alkyl groups        having 1 to 20 carbon atoms, and may include an ether group or        hydroxyl group. Further, X′s may be bonded to each other to form        a ring. Here, R³⁰⁰, R³⁰², and R³⁰⁵ are each a linear or branched        alkylene group having 1 to 4 carbon atoms; and R³⁰¹ and R³⁰⁴ are        each a hydrogen atom, or a linear, branched, or cyclic alkyl        group having 1 to 20 carbon atoms, and may include one or more        of hydroxyl group, ether group, ester group, and lactone ring.        R³⁰³ is a single bond, or a linear or branched alkylene group        having 1 to 4 carbon atoms; and R³⁰⁶ is a linear, branched, or        cyclic alkyl group having 1 to 20 carbon atoms, and may include        one or more of hydroxyl group, ether group, ester group, and        lactone ring.

Concrete examples of the compound represented by the general formula(B)-1 include:

-   -   tris(2-methoxymethoxyethyl)amine,        tris{2-(2-methoxyethoxy)ethyl}amine,        tris{2-(2-methoxyethoxymethoxy)ethyl}amine,        tris{2-(1-methoxyethoxy)ethyl}amine,        tris{2-(1-ethoxyethoxy)ethyl}amine, tris        {2-(1-ethoxypropoxy)ethyl}amine,        tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine,        4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane,        4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]eicosane,        1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane,        1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6,        tris(2-formyloxyethyl)amine, tris(2-acetoxyethyl)amine,        tris(2-propionyloxyethyl)amine, tris(2-butyryloxyethyl)amine,        tris(2-isobutyryloxyethyl)amine, tris(2-valeryloxyethyl)amine,        tris(2-pivaloyloxyethyl)amine,        N,N-bis(2-acetoxyethyl)-2-(acetoxyacetoxy)ethylamine,        tris(2-methoxycarbonyloxyethyl)amine,        tris(2-tert-butoxycarbonyloxyethyl)amine,        tris[2-(2-oxopropoxy)ethyl]amine,        tris[2-(methoxycarbonylmethyl)oxyethyl]amine,        tris[2-(tert-butoxycarbonylmethyloxy)ethyl]amine,        tris[2-(cyclohexyloxycarbonylmethyloxy)ethyl]amine,        tris(2-methoxycarbonylethyl)amine,        tris(2-ethoxycarbonylethyl)amine,        N,N-bis(2-hydroxyethyl)-2-(methoxycarbonyl)ethylamine,        N,N-bis(2-acetoxyethyl)-2-(methoxycarbonyl)ethylamine,        N,N-bis(2-hydroxyethyl)-2-(ethoxycarbonyl)ethylamine,        N,N-bis(2-acetoxyethyl)-2-(ethoxycarbonyl)ethylamine,        N,N-bis(2-hydroxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine,        N,N-bis(2-acetoxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine,        N,N-bis(2-hydroxyethyl)-2-(2-hydroxyethoxycarbonyl)ethylamine,        N,N-bis(2-acetoxyethyl)-2-(2-acetoxyethoxycarbonyl)ethylamine,        N,N-bis(2-hydroxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]-ethylamine,        N,N-bis(2-acetoxyethyl)-2-[(methoxycarbonypmethoxycarbonyl]-ethylamine,        N,N-bis(2-hydroxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine,        N,N-bis(2-acetoxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine,        N,N-bis(2-hydroxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)-ethylamine,        N,N-bis(2-acetoxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)-ethylamine,        N,N-bis(2-hydroxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxy-carbonyl]ethylamine,        N,N-bis(2-acetoxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxy-carbonyl]ethylamine,        N,N-bis(2-hydroxyethyl)-2-(4-hydroxybutoxycarbonyl)ethylamine,        N,N-bis(2-formyloxyethyl)-2-(4-formyloxybutoxycarbonyl)-ethylamine,        N,N-bis(2-formyloxyethyl)-2-(2-formyloxyethoxycarbonyl)-ethylamine,        N,N-bis(2-methoxyethyl)-2-(methoxycarbonyl)ethylamine,        N-(2-hydroxyethyl)-bis[2-(methoxycarbonyl)ethyl]amine,        N-(2-acetoxyethyl)-bis[2-(methoxycarbonyl)ethyl]amine,        N-(2-hydroxyethyl)-bis[2-(ethoxycarbonyl)ethyl]amine,        N-(2-acetoxyethyl)-bis[2-(ethoxycarbonyl)ethyl]amine,        N-(3-hydroxy-1-propyl)-bis[2-(methoxycarbonyl)ethyl]amine,        N-(3-acetoxy-1-propyl)-bis[2-(methoxycarbonyl)ethyl]amine,        N-(2-methoxyethyl)-bis[2-(methoxycarbonyl)ethyl]amine,        N-butyl-bis[2-(methoxycarbonyl)ethyl]amine,        N-butyl-bis[2-(2-methoxyethoxycarbonyl)ethyl]amine,        N-methyl-bis(2-acetoxyethyl)amine,        N-ethyl-bis(2-acetoxyethyl)amine,        N-methyl-bis(2-pivaloyloxyethyl)amine,        N-ethyl-bis[2-(methoxycarbonyloxy)ethyl]amine,        N-ethyl-bis[2-(tert-butoxycarbonyloxy)ethyl]amine,        tris(methoxycarbonylmethyl)amine,        tris(ethoxycarbonylmethyl)amine,        N-butyl-bis(methoxycarbonylmethyl)amine,        N-hexyl-bis(methoxycarbonylmethyl)amine, and        β-(diethylamino)-δ-valerolactone.

Further exemplified are the following nitrogen-containing organiccompounds having a ring structure represented by the following generalformula (B)-2:

-   -   wherein, X′ is described above; and R³⁰⁷ is a linear or branched        alkylene group having 2 to 20 carbon atoms, and may include one        or more of carbonyl group, ether group, ester group, and        sulfide.

Examples of compounds represented by the general formula (B)-2 include:1-[2-(methoxymethoxy)ethyl]pyrrolidine,1-[2-(methoxymethoxy)ethyl]piperidine,4-[2-(methoxymethoxy)ethyl]morpholine,1-[2-[(2-methoxyethoxy)methoxy]ethyl]pyrrolidine,1-[2-[(2-methoxyethoxy)methoxy]ethyl]piperidine,4-[2-[(2-methoxyethoxy)methoxy]ethyl]morpholine, 2-(1-pyrrolidinyl)ethylacetate, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate,2-(1-pyrrolidinyl)ethyl formate, 2-piperidinoethyl propionate,2-morpholinoethyl acetoxyacetate, 2-(1-pyrrolidinyl)ethylmethoxyacetate, 4-[2-(methoxycarbonyloxy)ethyl]morpholine,1-[2-(t-butoxycarbonyloxy)ethyl]piperidine,4-[2-(2-methoxyethoxycarbonyloxy)ethyl]morpholine, methyl3-(1-pyrrolidinyl)propionate, methyl 3-piperidinopropionate, methyl3-morpholinopropionate, methyl 3-(thiomorpholino)propionate, methyl2-methyl-3-(1-pyrrolidinyl)propionate, ethyl 3-morpholinopropionate,methoxycarbonylmethyl 3-piperidinopropionate, 2-hydroxyethyl3-(1-pyrrolidinyl)propionate, 2-acetoxyethyl 3-morpholinopropionate,2-oxotetrahydrofuran-3-yl 3-(1-pyrrolidinyl)propionate,tetrahydrofurfuryl 3-morpholinopropionate, glycidyl3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate,2-(2-methoxyethoxy)ethyl 3-(1-pyrrolidinyl)propionate, butyl3-morpholinopropionate, cyclohexyl 3-piperidinopropionate,α-(1-pyrrolidinyl)methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone,β-morpholino-δ-valerolactone, methyl 1-pyrrolidinylacetate, methylpiperidinoacetate, methyl morpholinoacetate, methylthiomorpholinoacetate, ethyl 1-pyrrolidinylacetate, 2-methoxyethylmorpholinoacetate, 2-morpholinoethyl 2-methoxyacetate, 2-morpholinoethyl2-(2-methoxyethoxy)acetate, 2-morpholinoethyl2-[2-(2-methoxyethoxy)ethoxy]acetate, 2-morpholinoethyl hexanoate,2-morpholinoethyl octanoate, 2-morpholinoethyl decanoate,2-morpholinoethyl laurate, 2-morpholinoethyl myristate,2-morpholinoethyl palmitate, and 2-morpholinoethyl stearate.

Further exemplified are the following nitrogen-containing organiccompounds each containing cyano group(s) represented by the followinggeneral formulae (B)-3 through (B)-6:

-   -   wherein, X′, R³⁰⁷, and n are described above; and R³⁰⁸ and R³⁰⁹        are the same or different linear or branched alkylene groups        having 1 to 4 carbon atoms.

Concrete examples of the nitrogen containing organic compoundsrepresented by the general formula (B)-3 through (B)-6 including a cyanogroup include 3-(diethylamino)propiononitrile,N,N-bis(2-hydroxyethyl)-3-aminopropiononitrile,N,N-bis(2-acetoxyethyl)-3-aminopropiononitrile,N,N-bis(2-formyloxyethyl)-3-aminopropiononitrile,N,N-bis(2-methoxyethyl)-3-aminopropiononitrile,N,N-bis[2-(methoxymethoxy)ethyl]-3-aminopropiononitrile, methylN-(2-cyanoethyl)-N-(2-methoxyethyl)-3-aminopropionate, methylN-(2-cyanoethyl)-N-(2-hydroxyethyl)-3-aminopropionate, methylN-(2-acetoxyethyl)-N-(2-cyanoethyl)-3-aminopropionate,N-(2-cyanoethyl)-N-ethyl-3-aminopropiononitrile,N-(2-cyanoethyl)-N-(2-hydroxyethyl)-3-aminopropiononitrile,N-(2-acetoxyethyl)-N-(2-cyanoethyl)-3-aminopropiononitrile,N-(2-cyanoethyl)-N-(2-formyloxyethyl)-3-aminopropiononitrile,N-(2-cyanoethyl)-N-(2-methoxyethyl)-3-aminopropiononitrile,N-(2-cyanoethyl)-N-[2-(methoxymethoxy)ethyl]-3-aminopropiononitrile,N-(2-cyanoethyl)-N-(3-hydroxy-1-propyl)-3-aminopropiononitrile,N-(3-acetoxy-1-propyl)-N-(2-cyanoethyl)-3-aminopropiononitrile,N-(2-cyanoethyl)-N-(3-formyloxy-1-propyl)-3-aminopropiononitrile,N-(2-cyanoethyl)-N-tetrahydrofurfuryl-3-aminopropiononitrile,N,N-bis(2-cyanoethyl)-3-aminopropiononitrile, diethylaminoacetonitrile,N,N-bis(2-hydroxyethyl)aminoacetonitrile,N,N-bis(2-acetoxyethyl)aminoacetonitrile,N,N-bis(2-formyloxyethyl)aminoacetonitrile,N,N-bis(2-methoxyethyl)aminoacetonitrile,N,N-bis[2-(methoxymethoxy)ethyl]aminoacetonitrile, methylN-cyanomethyl-N-(2-methoxyethyl)-3-aminopropionate, methylN-cyanomethyl-N-(2-hydroxyethyl)-3-aminopropionate, methylN-(2-acetoxyethyl)-N-cyanomethyl-3-aminopropionate,N-cyanomethyl-N-(2-hydroxyethyl)aminoacetonitrile,N-(2-acetoxyethyl)-N-(cyanomethyl)aminoacetonitrile,N-cyanomethyl-N-(2-formyloxyethyl)aminoacetonitrile,N-cyanomethyl-N-(2-methoxyethyl)aminoacetonitrile,N-cyanomethyl-N-[2-(methoxymethoxy)ethyl]aminoacetonitrile,N-(cyanomethyl)-N-(3-hydroxy-1-propyl)aminoacetonitrile,N-(3-acetoxy-1-propyl)-N-(cyanomethyl)aminoacetonitrile,N-cyanomethyl-N-(3-formyloxy-1-propyl)aminoacetonitrile,N,N-bis(cyanomethyl)aminoacetonitrile, 1-pyrrolidine propiononitrile,1-piperidine propiononitrile, 4-morpholine propiononitrile,1-pyrrolidine acetonitrile, 1-piperidine acetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, cyanomethylN,N-bis(2-hydroxyethyl)-3-aminopropionate, cyanomethylN,N-bis(2-acetoxyethyl)-3-aminopropionate, cyanomethylN,N-bis(2-formyloxyethyl)-3-aminopropionate, cyanomethylN,N-bis(2-methoxyethyl)-3-aminopropionate, cyanomethylN,N-bis[2-(methoxymethoxy)ethyl]-3-aminopropionate, 2-cyanoethyl3-diethylaminopropionate, 2-cyanoethylN,N-bis(2-hydroxyethyl)-3-aminopropionate, 2-cyanoethylN,N-bis(2-acetoxyethyl)-3-aminopropionate, 2-cyanoethylN,N-bis(2-formyloxyethyl)-3-aminopropionate, 2-cyanoethylN,N-bis(2-methoxyethyl)-3-aminopropionate, 2-cyanoethylN,N-bis[2-(methoxymethoxy)ethyl]-3-aminopropionate, cyanomethyl1-pyrrolidine propionate, cyanomethyl 1-piperidine propionate,cyanomethyl 4-morpholine propionate, 2-cyanoethyl 1-pyrrolidinepropionate, 2-cyanoethyl 1-piperidine propionate, and 2-cyanoethyl4-morpholine propionate.

Further exemplified are nitrogen-containing organic compounds having animidazole structure and a polar functional group, represented by thefollowing general formula (B)-7:

-   -   wherein R³¹⁰ is a linear, branched, or cyclic alkyl group having        2 to 20 carbon atoms and having one or more polar functional        groups, which is each a hydroxyl group, carbonyl group, ester        group, ether group, sulfide group, carbonate group, cyano group,        or acetal group; and    -   R³¹¹, R³¹², and R³¹³ are each a hydrogen atom, or a linear,        branched, or cyclic alkyl group, aryl group, or aralkyl group        having 1 to 10 carbon atoms.

Further exemplified are nitrogen-containing organic compounds having abenzimidazole structure and a polar functional group, as represented bythe following general formula (B)-8:

-   -   wherein R³¹⁴ is a hydrogen atom, or a linear, branched, or        cyclic alkyl group, aryl group, or aralkyl group having 1 to 10        carbon atoms; and    -   R³¹⁵ is a linear, branched, or cyclic alkyl group having 1 to 20        carbon atoms and having one or more polar functional groups,        which is each an ester group, acetal group, or cyano group,        wherein the alkyl group may additionally include one or more        hydroxyl groups, carbonyl groups, ether groups, sulfide groups,        or carbonate groups.

Further exemplified are nitrogen-containing heterocyclic compoundshaving a polar functional group(s), as represented by the followinggeneral formulae (B)-9 and (B)-10:

-   -   wherein A is a nitrogen atom, or ≡C—R³²²;    -   B is a nitrogen atom, or ≡C—R³²³;    -   R³¹⁶ is a linear, branched, or cyclic alkyl group having 2 to 20        carbon atoms and having one or more polar functional groups,        which is each a hydroxyl group, carbonyl group, ester group,        ether group, sulfide group, carbonate group, cyano group, or        acetal group;    -   R³¹⁷, R³¹⁸, R³¹⁹, and R³²⁰ are each a hydrogen atom, or a        linear, branched, or cyclic alkyl group or aryl group having 1        to 10 carbon atoms; or R³¹⁷ and R³¹⁸, R¹⁹ and R³²⁰ may be bonded        to each other to form a benzene ring, naphthalene ring, or        pyridine ring;    -   R³²¹ is a hydrogen atom, or a linear, branched, or cyclic alkyl        group or aryl group having 1 to 10 carbon atoms;    -   R³²² and R³²³ are each a hydrogen atom, or a linear, branched,        or cyclic alkyl group or aryl group having 1 to 10 carbon atoms;        and    -   R³²¹ and R³²³ may be bonded to each other to form a benzene ring        or naphthalene ring;    -   wherein the symbol “≡” does not represent a triple bond, and        simply represents three bonding orbitals, which are those bonds        to adjoining N and B here.

Further exemplified are nitrogen-containing organic compounds having anaromatic carboxylic acid ester structure, as represented by thefollowing general formulae (B)-11 through (B)-14:

-   -   wherein R³²⁴ is an aryl group having 6 to 20 carbon atoms or a        heteroaromatic group having 4 to 20 carbon atoms, wherein one,        some, or all of hydrogen atoms of the group may be each        substituted by a halogen atom, a linear, branched, or cyclic        alkyl group having 1 to 20 carbon atoms, an aryl group having 6        to 20 carbon atoms, an aralkyl group having 7 to 20 carbon        atoms, an alkoxy group having 1 to 10 carbon atoms, an acyloxy        group having 1 to 10 carbon atoms, or an alkylthio group having        1 to 10 carbon atoms;    -   R³²⁵ is CO₂R³²⁶, OR³²⁷, or a cyano group;    -   R³²⁶ is an alkyl group having 1 to 10 carbon atoms, wherein one        or some of methylene groups thereof may be each substituted by        an oxygen atom;    -   R³²⁷ is an alkyl group or acyl group having 1 to 10 carbon        atoms, wherein one or some of methylene groups thereof may be        each substituted by an oxygen atom;    -   R³²⁸ is a single bond, methylene group, ethylene group, sulfur        atom, or —O(CH₂CH₂O)_(n)— group, where n=0, 1, 2, 3, or 4;    -   R³²⁹ is a hydrogen atom, methyl group, ethyl group, or phenyl        group;    -   X″ is a nitrogen atom or CR³³⁰;    -   Y′ is a nitrogen atom or CR³³¹;    -   Z is a nitrogen atom or CR³³²;    -   R³³⁰, R³³¹, and R³³² are each independently a hydrogen atom,        methyl group, or phenyl group, or    -   R³³⁰ and R³³¹, or R³³¹ and R³³² may be bonded to each other to        form an aromatic ring having 6 to 20 carbon atoms or a        heteroaromatic ring having 2 to 20 carbon atoms.

Further exemplified are nitrogen-containing organic compounds having a7-oxanorbornane-2-carboxylic acid ester structure, as represented by thefollowing general formula (B)-15:

-   -   wherein R³³³ is a hydrogen atom, or a linear, branched, or        cyclic alkyl group having 1 to 10 carbon atoms;    -   R³³⁴ and R³³⁵ are each independently an alkyl group having 1 to        20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or        an aralkyl group having 7 to 20 carbon atoms, wherein some of        hydrogen atoms of the group may be each substituted by a halogen        atom, and wherein the group may have one or more polar        functional groups such as an ether, carbonyl, ester, alcohol,        sulfide, nitrile, amine, imine, amide, or the like; and    -   R³³⁴ and R³³⁵ may be bonded to each other to form a hetero ring        or heteroaromatic ring having 2 to 20 carbon atoms.

Further, it is also possible to utilize amine oxide compounds, which areoxides of the above described amine compounds, respectively. Note thatapplication of amine oxides as basic compounds is disclosed in JapanesePatent Application Laid-open (kokai) No. 2008-102383. Among them, aminecompounds represented by the following general formula (4) and amineoxide compounds, which are oxides thereof, can be desirably usedcombinedly with the above described amine compounds or amine oxidecompounds having a carboxyl group and having no hydrogen atomscovalently bonded to a nitrogen atom as a basic center:

-   -   wherein R₇, R₈, and R₉ are each a hydrogen atom, a linear,        branched, or cyclic alkyl group having 1 to 20 carbon atoms, an        aryl group having 6 to 20 carbon atoms, an aralkyl group having        7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon        atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an        acyloxyalkyl group having 2 to 10 carbon atoms, or an        alkylthio-alkyl group having 1 to 10 carbon atoms; and    -   two of R₇, R₈, and R₉ may be bonded to form a ring structure or        an aromatic ring.

The blending amount of the component (C) is preferably 0.01 to 2 parts(weight parts; and so forth), particularly 0.01 to 1 part relative to100 parts of the base resin as the component (A). Excessively smallamounts fail to exhibit blending effects, and excessively large amountsoccasionally lead to excessively deteriorated sensitivities.

To desirably achieve the effect of the present invention, it ispreferable to blend the component (C) at a blending ratio(weight/weight) in a range of 100:0 to 20:80 between (i) the abovedescribed amine compounds or amine oxide compounds having a carboxylgroup and having no hydrogen atoms covalently bonded to a nitrogen atomas a basic center, and (ii) the other amine compounds or amine oxidecompounds. Further, to achieve a higher level of obtainment of a stableresist pattern with a higher precision even under fluctuations such asin standing periods of time until exposure after formation of resistfilms, and in conditions of heating before exposure (prebaking), theamine compounds or amine oxide compounds having a carboxyl group andhaving no hydrogen atoms covalently bonded to a nitrogen atom as a basiccenter, are to be preferably added in amounts of 40 weight % or more ofthe total basic compounds.

To improve a coatability of the resist composition of the presentinvention, it is possible to add thereto a conventional surfactant (D),as an optional component in addition to the above enumerated components.Note that the optional component may be added in an ordinary amountwithin a range, which does not obstruct the effect of the presentinvention.

Examples of surfactants include, without particular limitation,

-   -   polyoxyethylene alkyl ethers such as polyoxyethylene lauryl        ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl        ether, and polyoxyethylene olein ether;    -   polyoxyethylene alkyl alyl ethers such as polyoxyethylene octyl        phenol ether, and polyoxyethylene nonyl phenol ether;    -   polyoxyethylene polyoxypropylene block copolymers;    -   sorbitan fatty acid esters such as sorbitan monolaurate,        sorbitan monopalmitate, and sorbitan monostearate;    -   nonionic surfactants of polyoxyethylene sorbitan fatty acid        ester, such as polyoxyethylene sorbitan monolaurate,        polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan        monostearate, polyoxyethylene sorbitan trioleate, and        polyoxyethylene sorbitan tristearate;    -   fluorinated surfactants such as F TOP EF301, EF303, EF352        (produced by JEMCO Inc.), MEGAFAC F171, F172, F173, R08, R30,        R90, R94 (produced by Dai-Nippon Ink & Chemicals, Inc.), Fluorad        FC-430, FC-431, FC-4430, FC-4432 (produced by Sumitomo 3M Co.,        Ltd.), ASAHIGUARD AG710, SURFLON S-381, S-382, S-386, SC101,        SC102, SC103, SC104, SC105, SC106, SURFINOL E1004, KH-10, KH-20,        KH-30, KH-40 (produced by Asahi Glass Co.);    -   organosiloxane polymers KP341, X-70-092, X-70-093 (produced by        Shin-Etsu Chemical Co., Ltd.); and    -   acrylic or methacrylic POLYFLOW No. 75, No. 95 (produced by        Kyoeisha Yushi Kagaku Kogyo Co., Ltd.); and    -   those surfactants are also preferably used, which are partially        fluorinated oxetane ring-opening polymers having the following        structure:

-   -   wherein R, Rf, A, B, C, m, and n are applied to the formula        (surf-1) only, irrespectively of the above descriptions        unrelated to surfactants. R represents an aliphatic group having        valence of 2 to 4 and having 2 to 5 carbon atoms, and concrete        examples thereof include: 1,4-butylene, 1,2-propylene,        2,2-dimethyl-1,3-propylene, 1,5-pentylene as divalent ones; and        those represented by the following formulae, as trivalent and        tetravalent ones:

-   -   wherein broken lines represent bonding hands, and the structures        are partial ones derived from glycerol, trimethylolethane,        trimethylolpropane, and pentaerythritol, respectively.

To be preferably used among them are 1,4-butylene, and2,2-dimethyl-1,3-propylene. Rf is a trifluoromethyl group orpentafluoroethyl group, and the trifluoromethyl group is preferable. mis an integer of 0 to 3, n is an integer of 1 to 4, and the sum of n andm indicates a valence of R and is an integer of 2 to 4. A is 1, Brepresents an integer of 2 to 25, and C represents an integer of 0 to10. Preferably, B represents an integer of 4 to 20, and C represents aninteger of 0 to 1. Further, constitutional units in the above structuresdo not define the order of them, and may be bonded in a block or randommanner. Production of surfactants based on partially fluorinated oxetanering-opening polymers, is detailed in U.S. Pat. No. 5,650,483. Desirableamong them are, FC-4430, SURFLON S-381, SURFINOL E1004, KH-20, KH-30,and the oxetane ring-opening polymers represented by the structuralformula. These can be used solely, or mixedly in two or more kinds.

The addition amount of the surfactant in the chemically amplified resistcomposition of the present invention, is 2 parts or less, and preferably1 part or less, relative to 100 parts of the base resin (A) in theresist composition.

The formation of a resist film onto a processing substrate by using theresist composition of the present invention, is carried out through astep of coating the resist composition onto the processing substrate,and a subsequent prebaking step, and these steps can be conducted byknown methods, respectively, to form resist films having thicknesses of10 to 2,000 nm depending on purposes.

Although some methods are known as the coating step in addition to spincoating, the spin coating is most desirable in order to obtain a uniformfilm thickness in case of forming resist films having thicknesses ofabout 150 nm, or thinner.

When the processing substrate is a semiconductor wafer, coatingconditions upon spin coating are required to be adjusted such asdepending on the size of the wafer, a targeted film thickness,composition of the resist composition, and the like. In case ofobtaining a resist film thickness of about 100 nm by adopting an 8-inchwafer (diameter of 200 mm), the resist composition is to be cast ontothe wafer, followed by rotation thereof at a revolution speed of 4,000to 5,000 rpm for 40 seconds, thereby enabling obtainment of a resistfilm higher in uniformity. Here, the usage amount of a solvent to beused upon preparation of the resist composition is 1,400 to 1,600 partsrelative to 100 parts of the base resin.

Further, the resist film obtained in the above manner is subjected toprebaking, so as to remove an excessive solvent remaining in the film.The conditions of prebaking are typically 80 to 130° C. for 1 to 10minutes, more desirably at 90 to 110° C. for 3 to 5 minutes, uponconduction on a hot plate.

When the processing substrate is a photomask blank, coating conditionsare also required to be adjusted such as depending on the size of theblank, a targeted film thickness, composition of the resist composition,and the like. In case of obtaining a resist film thickness of about 100nm on a rectangular blank of 15.2 cm×15.2 cm, the resist composition isto be cast onto the blank, followed by rotation thereof at a revolutionspeed of 1,500 to 3,000 rpm for 2 seconds and a subsequent rotation at800 rpm or less for 30 seconds, thereby enabling obtainment of a filmhigher in uniformity. Here, the usage amount of a solvent to be usedupon preparation of the resist composition is 2,000 to 2,700 partsrelative to 100 parts of the base resin.

Further, the resist film obtained in the above manner is subjected toprebaking, so as to remove an excessive solvent remaining in the film.The conditions of prebaking are typically 80 to 130° C. for 4 to 20minutes, more desirably at 90 to 110° C. for 8 to 12 minutes, uponconduction on a hot plate.

Next, pattern exposure is conducted for the above obtained resist film,for formation of an intended pattern. As an exposure method in case ofworking a semiconductor, there is held up a mask for forming theintended pattern above the resist film, followed by irradiationthereonto of high energy radiation such as deep ultraviolet rays,excimer laser, X-rays, or the like, or irradiation of electron beam, atan exposure value of 1 to 100 μC/cm², preferably 10 to 100 μC/cm². Inaddition to the typical exposure method, it is also possible to adopt animmersion method for exposure in a manner to achieve liquid immersionbetween a projection lens and a resist as required.

Further, in case of working a photomask blank, this is not to produceidentical items, so that pattern exposure is typically conducted by beamexposure. Although the high energy radiation to be used is typically anelectron beam, those high energy radiations are also usable, whichinclude beams from the above-described and other light sources.

To conduct a chemical amplification reaction by diffusing acidstypically after exposure, there is conducted post-exposure bake (PEB) at60 to 150° C. for 4 to 20 minutes, and preferably at 80 to 140° C. for 8to 12 minutes, on a hot plate, for example. There is then formed anintended pattern on the substrate by development in a usual manner suchas a dipping, puddling, spraying method, or the like for 0.1 to 3minutes, and preferably 0.5 to 2 minutes, by adopting 0.1 to 5 weight %,preferably 2 to 3 weight % of an aqueous alkaline developer such astetramethylammonium hydroxide (TMAH). It is also possible to conduct afurther heat treatment after development to thereby conduct a patternsize adjustment (i.e., thermal flow), as required. Note that the resistcomposition of the present invention is most suitable for finepatterning by deep ultraviolet rays or excimer laser at 250 to 120 nm,ultra-short ultraviolet, X-rays, and electron beams, among high energyradiations.

A Substrate to be processed of lithography, to which the resistpatterning process of the present invention is to be applied, may be anysubstrates insofar as subjected to utilization of lithography based onphotoresists, such as a semiconductor wafer, an intermediate substrateof semiconductor production, a photomask substrate, and the like, andthe effect of the present invention can be advantageously obtained incase of a substrate having a film of metal compound thereon formed by amethod such as sputtering. Among the above, the effect of the presentinvention is particularly useful in a photomask blank having anoutermost surface carrying thereon a chromium compound film formed as alight-shielding film or etching mask film, because it is difficult tocontrol a profile of a resist pattern near its boundary face on achromium compound of a chromium compound film. Examples of chromiumcompounds as materials at outermost surfaces of substrates to which thepresent invention is desirably applied, include metal chromium, chromiumoxide, chromium nitride, chromium carbide, chromium oxide nitride,chromium oxide carbide, chromium nitride carbide, chromium oxide nitridecarbide, and the like.

EXAMPLES

The present invention will be concretely explained by describingExamples and Comparative Examples, concerning the resist compositionincluding the amine compound or amine oxide compound having a carboxylgroup and having no hydrogen atoms covalently bonded to a nitrogen atomas a basic center, without limited to the Examples.

Shown below are structural formulae of base resins (Polymers 1 and 2)and acid generators (PAG-1, 2) as constituent materials of resistcompositions, used in the present invention. In the following Examples,Mw and Mn represent values determined relative to polystyrene standards,as measured by gel permeation chromatography (GPC).

-   -   Solvent (A): propylene glycol methyl ether acetate (PGMEA)    -   Solvent (B): ethyl lactate (EL)

Further, the following compounds are amine compounds or amine oxidecompounds having a carboxyl group and having no hydrogen atomscovalently bonded to a nitrogen atom as a basic center, and otherinapplicable basic compounds (Quenchers), used in Examples andComparative Examples, respectively.

-   -   Quencher-1: m-dimethylaminobenzoic acid    -   Quencher-2: p-diethylaminobenzoic acid    -   Quencher-3: p-dibutylaminobenzoic acid    -   Quencher-4: p-dihexylaminobenzoic acid    -   Quencher-5: 2-(4-(dibutylamino)-2-hydroxybenzoyl)benzoic acid    -   Quencher-6: 4-(dimethylamino)phenylacetic acid    -   Quencher-7: 1-piperidinepropionic acid    -   Quencher-9: p-aminobenzoic acid*    -   Quencher-9′; 2-quinolinecarboxylic acid*    -   Quencher-10: tris(2-(methoxymethoxy)ethyl)amine*    -   Quencher-11: oxide of tris(2-(methoxymethoxy)ethyl)amine*    -   Quencher-12: tetrabutylammonium acetate*    -   Quencher-13: 2-(4-morpholinyl)ethyl octanoate*    -   Quencher-14: 2-(1H-benzoimidazole-1-yl)ethyl benzoate*    -   Quencher-15: oxide of m-dimethylaminobenzoic acid    -   Quencher-16: oxide of p-diethylaminobenzoic acid    -   Quencher-17: oxide of p-dibutylaminobenzoic acid    -   Quencher-18: oxide of p-dihexylaminobenzoic acid *basic compound        other than: “amine compound having a carboxyl group and having        no hydrogen atoms covalently bonded to a nitrogen atom as a        basic center”; and “oxide of the amine compound”    -   Surfactant A: KH-20 (produced by Asahi Glass Co.)    -   Surfactant B: PF-636 (produced by Omnova Solutions Inc.)    -   Crosslinking agent 1: tetramethoxymethylglycoluril

Examples 1 to 6, and Comparative Examples 1 to 3

Resist compositions listed in Table 1 were dissolved in the listedsolvents, respectively, and the obtained resist compositions were eachfiltered by a filter of 0.04 μm size made of nylon resin, followed byspin coating of each resist solution at a revolution speed of 2,500 rpmonto a mask blank of 152 mm square having an outermost surface made ofchromium oxide nitride, into a coated thickness of 150 nm. Next, eachmask blank was baked for 10 minutes by a hot plate at 90° C. Measurementof a thickness of each obtained resist film was conducted by an opticalmeasurement device NanoSpec (manufactured by Nanometrics Incorporated).The measurement was conducted at 81 in-plane points of an applicableblank substrate except for an outer peripheral region from an outer edgeto an inner extent at a distance of 10 mm therefrom, so as to calculatean averaged film thickness and a film thickness range.

TABLE 1 Composition Com. Com. Com. (weight part) Ex. 1 Ex. 2 Ex. 3 Ex. 4Ex. 5 Ex. 6 Ex. 1 Ex. 2 Ex. 3 polymer-1 80 80 80 80 80 80 80 80 80 PAG-16 6 6 6 6 6 6 6 6 PAG-2 2 2 2 2 2 2 2 2 2 Quencher-1 0.2 — — — — — —Quencher-2 — 0.2 — — 0.1 0.1 — — — Quencher-3 — — 0.2 — — 0.1 — — —Quencher-4 — — — 0.2 0.1 — — — — Quencher-9 — — — — — — 0.2 — —Quencher-9′ — — — — — — — 0.2 — Quencher-11 — — — — — — — — 0.2Surfactant A 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 Solvent A 470470 470 470 470 470 470 470 470 Solvent B 1,100 1,100 1,100 1,100 1,1001,100 1,100 1,100 1,100

Further, exposure was conducted by an electron beam exposure apparatus(EBM5000 Acceleration Voltage 50 keV manufactured by NuFLARE Technology,Inc.), followed by conduction of baking (PEB: post-exposure baking) at110° C. for 10 minutes and subsequent development by aqueous solution of2.38% tetramethylammonium hydroxide, thereby allowing for obtainment ofpositive patterns (Examples 1 to 6, and Comparative Examples 1 to 3).

The obtained resist patterns were evaluated in the following manner.Assuming that an exposure value for resolving top and bottom of a 200 nmline-and-space pattern at a resolution of 1:1 was an optimum exposurevalue (sensitivity: Eop), a minimum line width of the line-and-spacepattern found to be separated at this exposure value was defined to be aresolution of the applicable evaluated resist. Further, the profile ofeach resolved resist pattern was observed at a cross-section of theresist by a scanning electron microscope, particularly in terms ofpresence or absence of footing at a substrate-side boundary face ofresist.

For line edge roughness, 3σ was calculated by measuring 50 points over 5μm in a longitudinal direction of a 100 nm line pattern (S-8840manufactured by Hitachi, Ltd.). Smaller values represent betterperformances. For prebaking temperature dependency, there was measured apattern dimension change when the prebaking temperature was raised by10° C. Further, there was calculated a pattern dimension change amountper 1° C.

Shown in Table 2 are evaluation results of resolution, patterncross-sectional profile, line edge roughness, and prebaking temperaturedependency. Although footing was not overcome in case of p-aminobenzoicacid having a hydrogen atom covalently bonded to a nitrogen atom as abasic center (Comparative Example 1), 2-quinolinecarboxylic acid havinga nitrogen atom included in an aromatic ring (Comparative Example 2),and an oxide of tris(2-(methoxymethoxy)ethyl)amine containing nocarboxyl groups (Comparative Example 3), excellent pattern profileswithout footing were obtained in Examples 1 through 6. Although Example1 exhibited a larger prebaking temperature dependency, its resolution,cross-sectional profile, and line edge roughness were within allowableranges, respectively.

TABLE 2 Prebaking Line edge temperature Resolution Cross-sectionalroughness dependency (μm) profile (footing) (nm) (nm/° C.) Ex. 1 0.07Good 4 3 Ex. 2 0.07 Good 4 0.5 or less Ex. 3 0.07 Good 4 0.5 or less Ex.4 0.07 Good 4 0.5 or less Ex. 5 0.07 Good 4 0.5 or less Ex. 6 0.07 Good4 0.5 or less Com. Ex. 1 0.10 Presence of footing 5 3 Com. Ex. 2 0.09Presence of footing 5 1 Com. Ex. 3 0.09 Presence of footing 5 0.5 orless

Example 7 to Example 15

Resist compositions listed in Table 3 were prepared, which included theamine compound having a carboxyl group and having no hydrogen atomscovalently bonded to a nitrogen atom as a basic center of the presentinvention, and the conventional amine compounds, and the patterningprocess of the present invention was performed for them in the samemanner as Examples 1 through 6 to conduct evaluation of resolutions andpattern profiles thereof. Results thereof are listed in Table 4. In allExamples, excellent resolutions, pattern profiles without footing, andexcellent line edge roughness were obtained.

TABLE 3 Composition (weight part) Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12Ex. 13 Ex. 14 Ex. 15 polymer-1 80 80 80 80 80 80 80 80 80 PAG-1 6 6 6 66 6 6 6 6 PAG-2 2 2 2 2 2 2 2 2 2 Quencher-2 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 Quencher-10 0.1 — — — — 0.05 — — — Quencher-11 — 0.1 — — — —0.05 0.05 0.05 Quencher-12 — — 0.1 — — 0.05 Quencher-13 — — — 0.1 — 0.05— 0.05 — Quencher-14 — — — — 0.1 0.05 — — Surfactant A 0.07 0.07 0.070.07 0.07 0.07 0.07 0.07 0.07 Solvent A 470 470 470 470 470 470 470 470470 Solvent B 1,100 1,100 1,100 1,100 1,100 1,100 1,100 1,100 1,100

TABLE 4 Cross- Prebaking sectional Line edge temperature Resolutionprofile roughness dependency (μm) (footing) (nm) (nm/° C.) Ex. 7  0.07Good 4 0.5 or less Ex. 8  0.07 Good 3 0.5 or less Ex. 9  0.07 Good 4 0.5or less Ex. 10 0.07 Good 4 0.5 or less Ex. 11 0.07 Good 3 0.5 or lessEx. 12 0.07 Good 4 0.5 or less Ex. 13 0.07 Good 3 0.5 or less Ex. 140.07 Good 4 0.5 or less Ex. 15 0.07 Good 3 0.5 or less

Example 16 to Example 24

Resist compositions listed in Table 5 were prepared, which included theamine compound having a carboxyl group and having no hydrogen atomscovalently bonded to a nitrogen atom as a basic center of the presentinvention, and the patterning process of the present invention wasperformed for them in the same manner as Examples 1 through 6 to conductevaluation of resolutions and pattern profiles thereof. Results thereofare listed in Table 6. Excellent results were obtained here also,similarly to the above.

TABLE 5 Composition (weight Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. part) 1617 18 19 20 21 22 23 24 polymer-1 80 80 80 80 80 80 80 80 80 PAG-1 6 6 66 6 6 6 6 6 PAG-2 2 2 2 2 2 2 2 2 2 Quencher-5 0.2 — — — 0.1 — 0.1 — —Quencher-6 0.2 — 0.1 — 0.1 — — — Quencher-7 — — 0.2 — — — — 0.1 0.1Quencher-10 — — — — — 0.1 0.1 — 0.1 Quencher-11 — — — 0.1 0.1 — 0.1 —Surfactant A 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 Solvent A 470470 470 470 470 470 470 470 470 Solvent B 1,100 1,100 1,100 1,100 1,1001,100 1,100 1,100 1,100

TABLE 6 Cross- Prebaking sectional Line edge temperature Resolutionprofile roughness dependency (μm) (footing) (nm) (nm/° C.) Ex. 16 0.07Good 4 0.5 or less Ex. 17 0.07 Good 3 0.5 or less Ex. 18 0.07 Good 4 0.5or less Ex. 19 0.07 Good 4 0.5 or less Ex. 20 0.07 Good 3 0.5 or lessEx. 21 0.07 Good 4 0.5 or less Ex. 22 0.07 Good 3 0.5 or less Ex. 230.07 Good 4 0.5 or less Ex. 24 0.07 Good 3 0.5 or less

Examples 25 to 30, Comparative Examples 4 to 6

Chemically amplified negative resist compositions listed in Table 7 wereprepared, which included the amine compound having a carboxyl group andhaving no hydrogen atoms covalently bonded to a nitrogen atom as a basiccenter of the present invention, and the patterning process of thepresent invention was then performed for them to conduct evaluation ofresolutions and pattern profiles thereof.

The patterning process was conducted in the same manner as Example 1,after coating each resist solution onto a mask blank by spin. Shown inTable 8 are evaluation results of resolution, pattern cross-sectionalprofile (presence or absence of undercut), line edge roughness, andprebaking temperature dependency.

TABLE 7 Composition Ex. Ex. Ex. Ex. Ex. Ex. Com. Com. Com. (weight part)25 26 27 28 29 30 Ex. 4 Ex. 5 Ex. 6 polymer-2 80 80 80 80 80 80 80 80 80PAG-1 8 8 8 8 8 8 8 8 8 PAG-2 2 2 2 2 2 2 2 2 2 Cross-linking 8.2 8.28.2 8.2 8.2 8.2 8.2 8.2 8.2 agent 1 Quencher-1 0.2 — — — — — —Quencher-2 — 0.2 — — 0.1 0.1 — — — Quencher-3 — — 0.2 — — 0.1 — — —Quencher-4 — — — 0.2 0.1 — — — — Quencher-9 — — — — — — 0.2 — —Quencher-9′ — — — — — — — 0.2 — Quencher-10 — — — — — — — — 0.2Surfactant A 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 Solvent A 470470 470 470 470 470 470 470 470 Solvent B 800 800 800 800 800 800 800800 800

TABLE 8 Cross- Prebaking sectional Line edge temperature Resolutionprofile roughness dependency (μm) (undercut) (nm) (nm/° C.) Ex. 25 0.07Good 4 3 Ex. 26 0.07 Good 4 0.5 or less Ex. 27 0.07 Good 4 0.5 or lessEx. 28 0.07 Good 4 0.5 or less Ex. 29 0.07 Good 4 0.5 or less Ex. 300.07 Good 4 0.5 or less Com. 0.12 Presence of 5 3 Ex. 4  undercut Com.0.10 Presence of 5 1 Ex. 5  undercut Com. 0.10 Presence of 5 0.5 or lessEx. 6  undercut

From the above result, it was proven that adoption of the resistcomposition of the present invention allowed for assurance of anexpected prebaking temperature dependency and for obtainment of animproved cross-sectional profile, particularly a fine pattern withoutundercut at a substrate-side boundary face of resist, also in case ofthe chemically amplified negative resist compositions, identically tothe positive resists. In Comparative Examples, fine patterns werecollapsed due to undercut.

Example 31 to Example 39

Resist compositions listed in Table 9 were prepared, which included theamine compound having a carboxyl group and having no hydrogen atomscovalently bonded to a nitrogen atom as a basic center of the presentinvention, and the conventional amine compounds, and the patterningprocess of the present invention was performed for them in the samemanner as Examples 25 through 30 to conduct evaluation of resolutionsand pattern profiles thereof. As listed in Table 10, pattern profileswere obtained without undercut, together with excellent resolutions andline edge roughness, in all Examples.

TABLE 9 Composition Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. (weight part) 3132 33 34 35 36 37 38 39 polymer-2 80 80 80 80 80 80 80 80 80 PAG-1 6 6 66 6 6 6 6 6 PAG-2 2 2 2 2 2 2 2 2 2 Cross-linking 8.2 8.2 8.2 8.2 8.28.2 8.2 8.2 8.2 agent 1 Quencher-2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1Quencher-10 0.1 — — — — 0.05 — — — Quencher-11 — 0.1 — — — — 0.05 0.050.05 Quencher-12 — — 0.1 — — 0.05 Quencher-13 — — — 0.1 — 0.05 — 0.05 —Quencher-14 — — — — 0.1 0.05 — — Surfactant A 0.07 0.07 0.07 0.07 0.070.07 0.07 0.07 0.07 Solvent A 470 470 470 470 470 470 470 470 470Solvent B 800 800 800 800 800 800 800 800 800

TABLE 10 Cross- Prebaking sectional Line edge temperature Resolutionprofile roughness dependency (μm) (undercut) (nm) (nm/° C.) Ex. 31 0.07Good 4 0.5 or less Ex. 32 0.07 Good 3 0.5 or less Ex. 33 0.07 Good 4 0.5or less Ex. 34 0.07 Good 4 0.5 or less Ex. 35 0.07 Good 3 0.5 or lessEx. 36 0.07 Good 4 0.5 or less Ex. 37 0.07 Good 3 0.5 or less Ex. 380.07 Good 4 0.5 or less Ex. 39 0.07 Good 3 0.5 or less

Example 40 to Example 48

Resist compositions listed in Table 11 were prepared, which included theamine compound having a carboxyl group and having no hydrogen atomscovalently bonded to a nitrogen atom as a basic center of the presentinvention, and the patterning process of the present invention wasperformed for them in the same manner as Examples 25 through 30 toconduct evaluation of resolutions and pattern profiles thereof. Resultsthereof are listed in Table 12. Excellent results were obtained herealso, similarly to the above.

TABLE 11 Composition Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. (weight part)40 41 42 43 44 45 46 47 48 polymer-2 80 80 80 80 80 80 80 80 80 PAG-1 66 6 6 6 6 6 6 6 PAG-2 2 2 2 2 2 2 2 2 2 Crosslinking 8.2 8.2 8.2 8.2 8.28.2 8.2 8.2 8.2 agent 1 Quencher-5 0.2 — — — 0.1 — 0.1 — — Quencher-60.2 — 0.1 — 0.1 — — — Quencher-7 — — 0.2 — — — — 0.1 0.1 Quencher-10 — —— — — 0.1 0.1 — 0.1 Quencher-11 — — — 0.1 0.1 — 0.1 — Surfactant A 0.070.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 Solvent A 470 470 470 470 470470 470 470 470 Solvent B 800 800 800 800 800 800 800 800 800

TABLE 12 Cross- Prebaking sectional Line edge temperature Resolutionprofile roughness dependency (μm) (undercut) (nm) (nm/° C.) Ex. 40 0.07Good 4 0.5 or less Ex. 41 0.07 Good 3 0.5 or less Ex. 42 0.07 Good 4 0.5or less Ex. 43 0.07 Good 4 0.5 or less Ex. 44 0.07 Good 3 0.5 or lessEx. 45 0.07 Good 4 0.5 or less Ex. 46 0.07 Good 3 0.5 or less Ex. 470.07 Good 4 0.5 or less Ex. 48 0.07 Good 3 0.5 or less

Example 26, and Example 49 to Example 51

Resist compositions listed in Table 13 were each prepared based onExample 26 in a manner to vary an amount of Quencher-2:p-diethylaminobenzoic acid, i.e., the amine compound having a carboxylgroup and having no hydrogen atoms covalently bonded to a nitrogen atomas a basic center of the present invention, and the patterning processof the present invention was performed for them in the same manner asExamples 25 through 30 to conduct evaluation of resolutions, patternprofiles, edge roughness, and electron beam sensitivity thereof. Resultsthereof are listed in Table 14.

TABLE 13 Composition Ex. Ex. Ex. Ex. (weight part) 26 49 50 51 polymer-280 80 80 80 PAG-1 8 8 8 8 PAG-2 2 2 2 2 Crosslinking agent 1 8.2 8.2 8.28.2 Quencher-2 0.2 0.5 1.0 1.5 Surfactant A 0.07 0.07 0.07 0.07 SolventA 470 470 470 470 Solvent B 800 800 800 800

TABLE 14 Line edge Electron beam Resolution Cross-sectional roughnesssensitivity (μm) profile (undercut) (nm) (μC/cm²) Ex. 26 0.07 Good 4 10Ex. 49 0.06 Good 3 14 Ex. 50 0.05 Good 2 23 Ex. 51 0.045 Good 1 36

Although increase of p-diethylaminobenzoic acid decreased electron beamsensitivity, resolution and edge roughness were remarkably improved.Since higher sensitivities are more excellent in view of throughput ofmask production, it is understood that a material composition can beoptimized based on a relationship among throughput, resolution, and edgeroughness.

Example 52 to Example 57

Resist compositions listed in Table 15 were prepared, which included theamine compound having a carboxyl group and having no hydrogen atomscovalently bonded to a nitrogen atom as a basic center of the presentinvention, and the patterning process of the present invention wasperformed for them in the same manner as Examples 25 through 30 toconduct evaluation of resolutions and pattern profiles thereof. Resultsthereof are listed in Table 16. In all Examples, excellent patternprofiles were obtained, together with excellent resolutions and edgeroughness. Further, Example 52 was obtained as a result of adopting anoxide of the amine used in Example 1, and the prebaking temperaturedependency thereof (nm/° C.) was improved. It was assumed that oxidationof the amine caused the oxide to be scarcely evaporated from the resistfilm.

TABLE 15 Composition Ex. Ex. Ex. Ex. Ex. Ex. (weight part) 52 53 54 5556 57 polymer-2 80 80 80 80 80 80 PAG-1 8 8 8 8 8 8 PAG-2 2 2 2 2 2 2Crosslinking 8.2 8.2 8.2 8.2 8.2 8.2 agent 1 Quencher-15 0.2 — — — — —Quencher-16 — 0.2 — — 0.2 0.2 Quencher-17 — — 0.2 — — — Quencher-18 — —— 0.2 — — Quencher-10 — — — — 0.2 — Quencher-11 — — — — — 0.2 SurfactantA 0.07 0.07 0.07 0.07 0.07 0.07 Solvent A 470 470 470 470 470 470Solvent B 800 800 800 800 800 800

TABLE 16 Cross- Prebaking sectional Line edge temperature Resolutionprofile roughness dependency (μm) (undercut) (nm) (nm/° C.) Ex. 52 0.07Good 4 2 Ex. 53 0.07 Good 4 0.5 or less Ex. 54 0.07 Good 4 0.5 or lessEx. 55 0.07 Good 4 0.5 or less Ex. 56 0.07 Good 4 0.5 or less Ex. 570.07 Good 4 0.5 or less

Example 58 to Example 63

Resist compositions listed in Table 17 were prepared, which included theamine compound having a carboxyl group and having no hydrogen atomscovalently bonded to a nitrogen atom as a basic center of the presentinvention, and the patterning process of the present invention wasperformed for them in the same manner as Examples 25 through 30 toconduct evaluation of resolutions and pattern profiles thereof. Here,the used surfactant B (PF-636) had the following structure. Resultsthereof are listed in Table 18.

Namely, the surfactant was3-methyl-3-(2,2,2-trifluoroethoxymethyl)oxetane/tetrahydrofuran/2,2-dimethyl-1,3-propanediolcopolymer (produced by Omnova Solutions Inc.).

-   -   wherein    -   a:(b+b′):(c+c′)=1:4 to 7:0.01 to 1 (molar ratio), and    -   weight-average molecular weight: 1,500.

TABLE 17 Composition (weight part) Ex. 58 Ex. 59 Ex. 60 Ex. 61 Ex. 62Ex. 63 polymer-2 80 80 80 80 80 80 PAG-1 8 8 8 8 8 8 PAG-2 2 2 2 2 2 2Crosslinking 8.2 8.2 8.2 8.2 8.2 8.2 agent 1 Quencher-15 0.2 — — — — —Quencher-16 — 0.2 — — 0.2 0.2 Quencher-17 — — 0.2 — — — Quencher-18 — —— 0.2 — — Quencher-10 — — — — 0.2 — Quencher-11 — — — — — 0.2 SurfactantB 0.07 0.07 0.07 0.07 0.07 0.07 Solvent A 470 470 470 470 470 470Solvent B 800 800 800 800 800 800

TABLE 18 Line edge Prebaking Resolution Cross-sectional roughnesstemperature (μm) profile (undercut) (nm) dependency (nm/° C.) Ex. 0.07Good 4 2 58 Ex. 0.07 Good 4 0.5 or less 59 Ex. 0.07 Good 4 0.5 or less60 Ex. 0.07 Good 4 0.5 or less 61 Ex. 0.07 Good 4 0.5 or less 62 Ex.0.07 Good 4 0.5 or less 63

Also from the results, excellent pattern profiles were obtained inaddition to excellent resolutions and line edge roughness, identicallyto above-described Examples.

Example 64 to Example 72

Resist compositions listed in Table 19 were prepared, which included theamine compound having a carboxyl group and having no hydrogen atomscovalently bonded to a nitrogen atom as a basic center of the presentinvention, and the conventional amine compounds, and the patterningprocess of the present invention was performed for them in the samemanner as Examples 25 through 30 to conduct evaluation of resolutionsand pattern profiles thereof. Results thereof are listed in Table 20.

TABLE 19 Composition (weight part) Ex. 64 Ex. 65 Ex. 66 Ex. 67 Ex. 68Ex. 69 Ex. 70 Ex. 71 Ex. 72 polymer-2 80 80 80 80 80 80 80 80 80 PAG-1 66 6 6 6 6 6 6 6 PAG-2 2 2 2 2 2 2 2 2 2 Crosslinking 8.2 8.2 8.2 8.2 8.28.2 8.2 8.2 8.2 agent 1 Quencher-3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1Quencher-10 0.1 — — — — 0.05 — — — Quencher-11 — 0.1 — — — — 0.05 0.050.05 Quencher-12 — — 0.1 — — 0.05 Quencher-13 — — — 0.1 — 0.05 — 0.05 —Quencher-14 — — — — 0.1 0.05 — — Surfactant A 0.07 0.07 0.07 0.07 0.070.07 0.07 0.07 0.07 Solvent A 470 470 470 470 470 470 470 470 470Solvent B 800 800 800 800 800 800 800 800 800

TABLE 20 Cross- Prebaking sectional Line edge temperature Resolutionprofile roughness dependency (μm) (undercut) (nm) (nm/° C.) Ex. 64 0.07Good 4 0.5 or less Ex. 65 0.07 Good 3 0.5 or less Ex. 66 0.07 Good 4 0.5or less Ex. 67 0.07 Good 4 0.5 or less Ex. 68 0.07 Good 3 0.5 or lessEx. 69 0.07 Good 4 0.5 or less Ex. 70 0.07 Good 3 0.5 or less Ex. 710.07 Good 4 0.5 or less Ex. 72 0.07 Good 3 0.5 or less

As listed in Table 20, pattern profiles without undercut were obtainedfrom all Examples, together with excellent resolutions and line edgeroughness.

The present invention is not limited to the above embodiments. The aboveembodiments are merely illustrative, and whatever having thesubstantially same configurations as the technical concept recited inthe claims of the present application and exhibiting the same functionsand effects are embraced within the technical scope of the presentinvention.

What is claimed is:
 1. A resist patterning process comprising: coating achemically amplified resist composition onto a photomask blank having achromium compound film at an outermost surface, and heating thechemically amplified resist composition to eliminate an excessivesolvent component remaining in the coated film, to obtain a resist film;conducting pattern exposure on the resist film by high energy radiation;and developing the resist film with a developer, wherein the chemicallyamplified resist composition comprises one or more kinds of aminecompounds at least having: a carboxyl group; no hydrogen atomscovalently bonded to a nitrogen atom as a basic center; and no nitrogenatoms as part of an aromatic ring, and wherein the amine compound havinga carboxyl group and no hydrogen atoms covalently bonded to a nitrogenatom as a basic center is an amine compound represented by the followinggeneral formula (1):

wherein R₁ and R₂ are each a linear, branched, or cyclic alkyl grouphaving 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl grouphaving 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbonatoms, an acyloxyalkyl group having 2 to 10 carbon atoms, or analkylthio-alkyl group having 1 to 10 carbon atoms; R₁ and R₂ may bebonded to each other to form a ring structure; R₃ is a hydrogen atom, alinear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, anaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20carbon atoms, a hydroxyalkyl group having 2 to 10 carbon atoms, analkoxyalkyl group having 2 to 10 carbon atoms, an acyloxyalkyl grouphaving 2 to 10 carbon atoms, an alkylthio-alkyl group having 1 to 10carbon atoms, or a halogen group; and R₄ is a single bond or a linear,branched, or cyclic alkylene group having 1 to 20 carbon atoms, or anarylene group having 6 to 20 carbon atoms.
 2. The resist patterningprocess according to claim 1, wherein the chemically amplified resistcomposition further comprises one or more kinds of amine compounds eachrepresented by the following general formula (4):

wherein R₇, R₈, and R₉ are each a hydrogen atom, a linear, branched, orcyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, ahydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl grouphaving 2 to 10 carbon atoms, an acyloxyalkyl group having 2 to 10 carbonatoms, or an alkylthio-alkyl group having 1 to 10 carbon atoms, and twoof R₇, R₈ , and R₉ may be bonded to form a ring structure or an aromaticring.
 3. The resist patterning process according to claim 1, wherein thechemically amplified resist composition further comprises one or morekinds of amine oxide compounds each represented by the following generalformula (5):

wherein R₇, R₈, and R₉ are each a hydrogen atom, a linear, branched, orcyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, ahydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl grouphaving 2 to 10 carbon atoms, an acyloxyalkyl group having 2 to 10 carbonatoms, or an alkylthio-alkyl group having 1 to 10 carbon atoms, and twoof R₇, R₈, and R₉ may be bonded to form a ring structure or an aromaticring.
 4. The resist patterning process according to claim 1, wherein thechemically amplified resist composition further comprises, as maincomponents: (A1) a base resin insoluble or hardly soluble in alkali,having an acidic functional group protected by an acid labile group, theresin can be made soluble in alkali when the acid labile group iseliminated; and (B) an acid generator.
 5. The resist patterning processaccording to claim 2, wherein the chemically amplified resistcomposition further comprises, as main components: (A1) a base resininsoluble or hardly soluble in alkali, having an acidic functional groupprotected by an acid labile group, the resin can be made soluble inalkali when the acid labile group is eliminated; and (B) an acidgenerator.
 6. The resist patterning process according to claim 3,wherein the chemically amplified resist composition further comprises,as main components: (A1) a base resin insoluble or hardly soluble inalkali, having an acidic functional group protected by an acid labilegroup, the resin can be made soluble in alkali when the acid labilegroup is eliminated; and (B) an acid generator.
 7. The resist patterningprocess according to claim 1, wherein the chemically amplified resistcomposition further comprises, as main components: (A2) a base resin,which is soluble in alkali and which can be made insoluble in alkaliwith the aid of an acid catalyst, and/or a combination of a base resinwith a crosslinking agent, which base resin is soluble in alkali and canbe made insoluble in alkali via reaction with the crosslinking agentwith the aid of an acid catalyst; and (B) an acid generator.
 8. Theresist patterning process according to claim 2, wherein the chemicallyamplified resist composition further comprises, as main components: (A2)a base resin, which is soluble in alkali and which can be made insolublein alkali with the aid of an acid catalyst, and/or a combination of abase resin with a crosslinking agent, which base resin is soluble inalkali and can be made insoluble in alkali via reaction with thecrosslinking agent with the aid of an acid catalyst; and (B) an acidgenerator.
 9. The resist patterning process according to claim 3,wherein the chemically amplified resist composition further comprises,as main components: (A2) a base resin, which is soluble in alkali andwhich can be made insoluble in alkali with the aid of an acid catalyst,and/or a combination of a base resin with a crosslinking agent, whichbase resin is soluble in alkali and can be made insoluble in alkali viareaction with the crosslinking agent with the aid of an acid catalyst;and (B) an acid generator.
 10. A resist patterning process comprising:coating a chemically amplified resist composition onto a photomask blankhaving a chromium compound film at an outermost surface, and heating thechemically amplified resist composition to eliminate an excessivesolvent component remaining in the coated film, to obtain a resist film;conducting pattern exposure on the resist film by high energy radiation;and developing the resist film with a developer, wherein the chemicallyamplified resist composition comprises one or more kinds of aminecompounds at least having: a carboxyl group; no hydrogen atomscovalently bonded to a nitrogen atom as a basic center; and no nitrogenatoms as part of an aromatic ring, and the nitrogen atom of the aminecompound has three single bonds combined to different carbon atoms,respectively, wherein the chemically amplified resist compositionfurther comprises one or more kinds of amine oxide compounds eachrepresented by the following general formula (5):

wherein R₇, R₈, and R₉ are each a hydrogen atom, a linear, branched, orcyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, ahydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl grouphaving 2 to 10 carbon atoms, an acyloxyalkyl group having 2 to 10 carbonatoms, or an alkylthio-alkyl group having 1 to 10 carbon atoms, and twoof R₇, R₈, and R₉ may be bonded to form a ring structure or an aromaticring.
 11. The resist patterning process according to claim 10, whereinthe amine compound having a carboxyl group and no hydrogen atomscovalently bonded to a nitrogen atom as a basic center is an aminecompound represented by the following general formula (3):

wherein R₅ is a linear or branched substitutable alkylene group having 2to 20 carbon atoms that may include, between its carbon atoms, one ormore carbonyl groups, ether groups, ester groups, or sulfides, and R₆ isa linear, branched, or cyclic alkylene group having 1 to 20 carbonatoms, or an arylene group having 6 to 20 carbon atoms.
 12. The resistpatterning process according to claim 11, wherein the chemicallyamplified resist composition further comprises one or more kinds ofamine compounds each represented by the following general formula (4):

wherein R₇, R₈, and R₉ are each a hydrogen atom, a linear, branched, orcyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, ahydroxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkyl grouphaving 2 to 10 carbon atoms, an acyloxyalkyl group having 2 to 10 carbonatoms, or an alkylthio-alkyl group having 1 to 10 carbon atoms, and twoof R₇, R₈ , and R₉ may be bonded to form a ring structure or an aromaticring.
 13. The resist patterning process according to claim 11, whereinthe chemically amplified resist composition further comprises, as maincomponents: (A1) a base resin insoluble or hardly soluble in alkali,having an acidic functional group protected by an acid labile group, theresin can be made soluble in alkali when the acid labile group iseliminated; and (B) an acid generator.
 14. The resist patterning processaccording to claim 12, wherein the chemically amplified resistcomposition further comprises, as main components: (A1) a base resininsoluble or hardly soluble in alkali, having an acidic functional groupprotected by an acid labile group, the resin can be made soluble inalkali when the acid labile group is eliminated; and (B) an acidgenerator.
 15. The resist patterning process according to claim 10,wherein the chemically amplified resist composition further comprises,as main components: (A1) a base resin insoluble or hardly soluble inalkali, having an acidic functional group protected by an acid labilegroup, the resin can be made soluble in alkali when the acid labilegroup is eliminated; and (B) an acid generator.
 16. The resistpatterning process according to claim 11, wherein the chemicallyamplified resist composition further comprises, as main components: (A2)a base resin, which is soluble in alkali and which can be made insolublein alkali with the aid of an acid catalyst, and/or a combination of abase resin with a crosslinking agent, which base resin is soluble inalkali and can be made insoluble in alkali via reaction with thecrosslinking agent with the aid of an acid catalyst; and (B) an acidgenerator.
 17. The resist patterning process according to claim 12,wherein the chemically amplified resist composition further comprises,as main components: (A2) a base resin, which is soluble in alkali andwhich can be made insoluble in alkali with the aid of an acid catalyst,and/or a combination of a base resin with a crosslinking agent, whichbase resin is soluble in alkali and can be made insoluble in alkali viareaction with the crosslinking agent with the aid of an acid catalyst;and (B) an acid generator.
 18. The resist patterning process accordingto claim 10, wherein the chemically amplified resist composition furthercomprises, as main components: (A2) a base resin, which is soluble inalkali and which can be made insoluble in alkali with the aid of an acidcatalyst, and/or a combination of a base resin with a crosslinkingagent, which base resin is soluble in alkali and can be made insolublein alkali via reaction with the crosslinking agent with the aid of anacid catalyst; and (B) an acid generator.